CN108291049A

CN108291049A - With silica enhance elastomeric compound and include its product

Info

Publication number: CN108291049A
Application number: CN201680053417.1A
Authority: CN
Inventors: J.熊; M.C.格林; W.R.威廉斯; D.福米切夫; G.D.阿德勒; D.G.麦克唐纳; R.格罗希
Original assignee: Cabot Corp
Current assignee: Cabot Corp
Priority date: 2015-07-15
Filing date: 2016-07-13
Publication date: 2018-07-17
Anticipated expiration: 2036-07-13
Also published as: US20170306108A1; US10301439B2; WO2017011570A1; CA2992267A1; CN108291049B; FR3038901A1; GB2556570A; US20190375901A1; FR3038900A1; JP2018524450A; BR112018000834A2; GB201801671D0; RU2018105498A3; BR112018000831A2; IT201600073198A1; MY186076A; US9926413B2; JP2018528283A; GB2556568B; RU2703619C2

Abstract

Silica elastomeric compound with excellent mechanical properties.

Description

With silica enhance elastomeric compound and include its product

The present invention relates to silica elastomeric compounds.It is more particularly related to formed by wet method mother material The elastomeric compound enhanced through silica.

There is many product of commercial significance to be formed by elastic composition, wherein granular reinforcing material is scattered in various conjunctions In elastomer-forming, natural rubber or elastomer blend, for example, carbon black and silica are in natural rubber and other elastomers It is widely used as Contrast agent.Usually production masterbatch, that is, reinforcing material, elastomer and various optional additive (such as increments Oil) premix.There is many product of commercial significance to be formed by such elastic composition.Such product includes example Such as vehicle tyre, wherein different elastic compositions can be used for tread portion, side wall, serif covering and carcass.Other products Including for example, engine support bushing, conveyer belt, windscreen wiper, sealer, liner, wheel, buffer etc..

For a period of time, fine dispersion body of the particulate reinforcement reagent in Rubber compound have been considered as realizing One of good quality and most important object of consistent properties of product, also, sizable effort has been working on exploitation and uses In the method for improving dispersion quality.Masterbatch and other hybrid manipulations have a direct impact mixing efficiency and dispersion quality.One As for, for example, when carbon black in dry-mixed combination master batch for when enhancing rubber, can often realize acceptable carbon black macroscopic view point Granular media.However, bringing difficulty via the high-quality homogeneous dispersion of the silica of dry mixing process, also, industrially have been presented for Various solutions solve the problems, such as this, for example, the flowable particle form with " silica for capableing of high degree of dispersion " or " HDS " Precipitated silica.Stronger mixing can improve silica dispersion, but can also make the elastomer hair for being wherein dispersed with filler Raw degradation.For mechanical/thermal degrade highly sensitive natural rubber in the case of, this is especially problematic.

Other than Dry mixing techniques, it is known that stir elastomer latices or polymer solution and carbon black or silica slurry addition It mixes in tank.Such " wet method masterbatch " technology can be with natural rubber latex and emulsified synthetic elastomer such as styrene fourth Diene rubber (SBR) is used together.Although however, the Wet technique filler be carbon black when had shown that hope, When filler is silica, which brings challenge for obtaining acceptable elastomeric compound.For producing wet method mother The particular technique (such as technology disclosed in United States Patent (USP) No.6,048,923 (its content is incorporated herein by reference)) of material It is not efficiently used for producing elastomeric compound as solely or mainly Contrast agent using silica granule.

Therefore, it is necessary to use silica granule to be produced as solely or mainly Contrast agent and show improved engineering properties Elastomeric compound and vulcanized elastomeric compound.

Invention content

The invention is characterized in that using allowing what silica used to produce elastomeric compound based on the technique of liquid, and Still obtain required silica elastomeric compound.Silica granule being uniformly distributed by using stabilization removal in elastomer matrix Silica slurry and the continuous processings of elastomer latices realize.The silicon in elastomer latices is adjusted by forming rubber network The ratio of the liquid dispersion of stone causes the continuous rubber phase of the unique silica containing solid-state or semisolid, one kind to be dispersed in The cohesion mixture of silica in elastomer latices.The dehydration of continuous rubber phase containing silica generates silica elastomeric compound, When with processing is mixed to form vulcanized elastomeric compound, improved enhancing performance is generated.

In one embodiment, the present invention relates to the elastomeric compounds for using wet method masterbatch technique productions comprising, But it is not limited to, including the dispersion of the use of the fluid of elastomer latices and the stabilization removal comprising particle shape silica is additional Fluid use.Two kinds of fluids are combined under continuous flow condition and selected speed.The combination makes silica disperse In elastomer latices, also, parallel (or almost parallel), so that elastomer latices is converted to solid-state or semisolid from liquid Elastomeric compound, such as be converted to the continuous rubber phase of the silica containing solid-state or semisolid.For example, this can at about 2 seconds or Occur in shorter time (such as part second), this is because a fluid is with another fluid of enough energy impacts, So as to cause the uniform and close distribution of silica granule in the elastomer.The stabilization removal of silica is used in the masterbatch technique Dispersion can form the elastomeric compound with required characteristic.

The invention further relates to the elastomers formed by any one or more of wet method masterbatch technique as described herein to answer Close object.The product of elastomeric compound of the invention is made or included the invention further relates to the elastomeric compound by the present invention.

Understand, foregoing general description and following detailed description be merely exemplary with it is explanatory, and be intended to The claimed invention is explained further in offer.

Be attached to the attached drawing in the application and constituted part of this application show the present invention various features, and with Specification principle for explaining the present invention together.

Description of the drawings

Fig. 1 (a), 1 (b) and 1 (c) are that explanation can be used for preparing the elastomer according to embodiments of the present invention that can vulcanize Compound and the figure of exemplary hybrid devices used in some embodiments.

Fig. 2 is to form the elastomeric compound according to embodiments of the present invention that can vulcanize and vulcanized elastomer The block diagram of various steps that compound and while manufacturing Rubber compound using such elastomeric compound may occur.

Fig. 3 is to illustrate the engineering properties of various vulcanized silica elastomeric compounds relative to silica loading capacity (phr) series of drawing (Fig. 3 A-T300/T100 modular ratios, Fig. 3 B- tensile strengths (MPa), Fig. 3 C-tan δ 60 and Fig. 3 D- fractures Elongation (%) * tensile strengths (MPa))；Star：Pass through the elastomeric compound of dry-mixed production；Triangle：By intermittent The elastomeric compound of technique productions based on liquid；Diamond shape：According to the elastomeric compound of exemplary implementation scheme.

Fig. 4 depicts modular ratio (T300/T100) of the following substance relative to 60 values of tan δ：Sample (the star of comparative example 1 Shape), comparative example 8 operation 1-4 vulcanized elastomeric compound (triangle) and embodiment 5 vulcanized elastomer Compound (diamond shape).

Fig. 5 depicts modular ratio (T300/ of the vulcanized elastomeric compound relative to expansion index of embodiment 5 T100；Diamond shape) and tan δ 60 (square).

Fig. 6 depicts the vulcanized elastomeric compound (diamond shape) of embodiment 10 and sample (star) phase of comparative example 1 For the modular ratio (T300/T100) of silica loading capacity.

Specific implementation mode

In one embodiment, the elastomeric compound that can vulcanize includes to be dispersed in natural rubber at least The silica of 40phr.Silica can include precipitated silica, consisting essentially of or be made from it.When the elastomer that can vulcanize When compound cures, the T300/T100 ratios of obtained sulfur product are at least -0.024s+b, wherein s is elastomer The amount (rubber (phr) for being expressed as the weight of part/100) and b of silica in compound masterbatch are 6.3, and with selected from following At least one additional property：A) the tan δ 60 of at most 0.0022s-c, wherein c are 0.05；B) at least stretching of -0.21s+d Intensity (MPa), wherein d are 41；C) at least elongation at break of -211s+e (%) * tensile strengths (MPa), wherein e=27543, And d) the silica loading capacity of at least 55phr (for example, at least 60phr).Selectively, or in addition, b can be 6.4,6.6 or 6.8, C can be that 0.06 and/or d can be 41.4.For example, T300/T100 can be -0.024s+b to 7, tan δ 60 can be 0.02 to 0.0022s-c, tensile strength can be -0.21s+d to 35 or 40 and/or elongation at break (%) * tensile strengths (MPa) can be - 211s+e to 21500.

Selectively, or furthermore it is possible to the elastomeric compound of vulcanization includes the silica being dispersed in natural rubber, example Such as, the silica of at least 40 or 55phr.Silica can include precipitated silica, consisting essentially of or be made from it.When can When the elastomeric compound of vulcanization cures, obtained sulfur product shows at least 5.5 T300/T100 ratios and at most 0.05 tan δ 60.In another embodiment, the elastomeric compound that can vulcanize is dispersed in day comprising at least 55phr Silica in T PNR；When the elastomeric compound that can vulcanize cures, at least about 5 T300/T100 ratios are shown Rate.In another embodiment, including the elastomeric compound that can vulcanize for the silica being dispersed in natural rubber has At least 6.3 T300/T100 modular ratios.In another embodiment, the elastomeric compound that can vulcanize includes to be dispersed in At least 40phr for example, at least silicas of 50phr in natural rubber.When the elastomeric compound that can vulcanize cures, T300/T100 ratios at least -0.025s+6.2 (for example, at least -0.025s+6.3 or 6.4).The elasticity that can vulcanize Nanocrystal composition can include the dehydration wet method masterbatch that silica in fresh latex is dispersed in as slurry, can for example using Ammonia, removal sludge or chemistry or enzyme modification and being stabilized.

In another embodiment, the continuous rubber phase product of the silica containing solid-state includes to be dispersed in the natural rubber through cohesion (it can be formed or by precipitation silicon at least silica of 40phr in glue latex comprising precipitated silica, substantially by precipitated silica Stone forms).The continuous rubber phase product of the silica containing solid-state shows at least 100% elongation at break.

It, will by continuous method using fast wet masterbatch technique in the preferred method for the elastomeric compound that production can vulcanize Silica selectively and is strategically introduced into elastomer latices.The process can be in semiclosed reaction zone (for example, being suitable for Implement the tubular mixing chamber room of the device of such process or other mixing chamber under controlled volume flow and speed parameter) Middle progress causes if the selection of not silica and the strategic benefit performance that cannot achieve if.Further such as this paper It explains in detail, by " selection ", this method uses the dispersion of the stabilization removal of silica.Also, by " strategically " drawing Enter, it includes elastomer latices that preferred method, which uses at least two separated fluids, a kind of fluid, and one other fluid includes silica Stabilization removal dispersion.Two kinds of fluids can be pumped into or are transferred in reaction zone (such as semiclosed reaction zone).Two kinds Fluid can combine under the conditions of continuous flow and under selected volume flow and velocity conditions.Using selected differential degree The combination under stress of condition has enough energy so that silica can be in two seconds or less time (such as several In millisecond) it is distributed in elastomer latices, and elastomer latices are transformed into solid phase from liquid, for example, being transformed into containing solid The silica elastomeric compound of the form of state or the continuous rubber phase of semisolid silica.

The preferred production process for the silica elastomeric compound that can vulcanize may include following steps, substantially by following step Suddenly it forms, comprise the steps of or includes the following steps：

(a) provide comprising silica stabilization removal dispersion at least first fluid continuous flow under stress and The continuous flow of second fluid comprising elastomer latices is provided；

(b) adjusting the volume flow of first fluid and second fluid to generate there is about 15phr~about 180phr silicas to contain The elastomeric compound of amount；With

(c) enough impacts are used, first fluid stream and second fluid stream are combined (such as in semiclosed reaction zone In), to silica is distributed in elastomer latices, the continuous rubber phase to obtain the silica containing solid-state or silica containing semisolid Continuous rubber phase stream.Elastomer latices are transformed into the continuous rubber phase of the silica containing solid-state or semisolid by this method from liquid Stream.Continuous the substantially continuous of rubber phase that continuous rubber phase containing silica can be used as the silica containing solid-state or semisolid flows into Row is collected.

The additional improvement of engineering properties with below in connection with：The use of latex concentration object, silica slurry are gone using salt It stabilizes, with or without additional acid and vulcanized elastomeric compound about 1.80~about 2.20 (for example, about 1.90 ~about 2.10 or about 1.95~expansion index about 2.05).

The more details and/or option for producing the elastomeric compound that can vulcanize are described below.

As used in this article, " silica " refers to particle shape silica or the particle that is coated with silicon oxide, and includes Any type of precipitated silica, for example, polymolecularity (HDS) particle, non-HDS particles, silica aggregation and silica granule；Colloid Silica；Fumed silica；And their arbitrary combination.Such silica or the particle that is coated with silicon oxide may by Chemical treatment is to include the functional group for being combined (connection (such as being connected chemically) or adherency (such as absorption)) with silica surface.Cause This, " silica " includes appointing with the surface constituted substantially by silica or with the silica for being coupled or connected to functional group thereon What particle.

As used in this article, " dispersion " refers to stable suspension of the solid particle in aqueous fluids, wherein Charge at grain surface prevents particle aggregation, also, dispersion is characterized in that zeta potential magnitude is greater than or equal to 30mV.

Zeta potential is used to measure the stability of the charged particle (such as silica granule) of dispersion in a fluid.The measurement of zeta potential Can be with the variation of for example +/- 2mV, also, as used in this article, zeta potential magnitude refers to the absolute value of numerical value, example Such as, compared with the zeta potential value of -10mV, the zeta potential value of -30mV has the magnitude of bigger.

As used in this article, " dispersion of stabilization removal " refers to suspension of the solid particle in aqueous fluids, In, the charge at particle surface is reduced due to the presence of reagent or by the processing of solid particle, and its feature exists In zeta potential magnitude or more preferably less than 28mV or less than the zeta potential of 25mV less than 30mV.Aqueous fluids can be water, can be with The miscible fluid of water (such as alcohol or ether) partly fluid miscible with water or can at least contain miscible with water or can portion Divide the fluid mixture of fluid miscible with water.

As used in this article, term " silica slurry " and " dispersion " refer to dispersion of the silica in aqueous fluids, Wherein, the charge at silica surface prevents particle aggregation, also, dispersion is characterized in that the ζ electricity that magnitude is at least 30mV Gesture value.Silica slurry or dispersion can be by being handled or by handling silica by stabilization removal, to reduce with enough reagents Charge in silica surface, also, the feature of the silica slurry (or silica dispersion of stabilization removal) of the stabilization removal of gained It is less than the zeta potential magnitude of 30mV.

As used in this article, routinely, to those skilled in the art, term " uniform " and " equably " purport In the concentration and the group for indicating the component (such as particle filler) with any given volume fraction or percentage (such as 5%) Concentration point in the total volume for the material (such as elastomeric compound or dispersion) studied is identical, and (such as deviation is no more than 2%).If necessary, those skilled in the art will by using from different location (such as near surface or ontology Higher depth) if the concentration of component measurement result of the dry-eye disease obtained verifies the statistics uniformity of material.

As used in this article, " silica elastomeric compound " refer to containing enhancing amount (for example, about 15phr~about Masterbatch (reinforcing material, elastomer and various of the coherent rubber (coherent rubber) of dispersion silica 180phr) The premix of the additive (such as extending oil) of choosing).Silica elastomeric compound can contain optional further component, example Such as, other grains of acid, salt, antioxidant, antidegradant, coupling agent, small amount (for example, 10wt% of all particles or lower) Son, processing aid, and/or extending oil or its arbitrary combination.

As used in this article, " the continuous rubber phase of the silica containing solid-state " refers to have continuous rubber phase and silica uniform Dispersed phase and for example be up to 90wt% aqueous fluids compound.The continuous rubber phase of the silica containing solid-state can have continuous The form of rope or worm.Upon compression, these articles release water outlet.The continuous rubber phase of the silica containing solid-state can contain optional Further component, for example, acid, salt, antioxidant, coupling agent, small amount (for example, 10wt% of all particles or lower) Other particles, and/or processing oil or its arbitrary combine.

As used in this article, " the continuous rubber phase of the silica containing semisolid " refers to having the continuous rubber phase containing silica Compound with pasty consistency.The semisolid product has the continuous phase of rubber, with being evenly distributed in entire rubber phase The silica being captured.When with one or many subsequent operations, (it is selected for paste or gelatinous Materials At the continuous rubber phase of the silica containing solid-state) come when further processing, the continuous rubber phase of the silica containing semisolid keeps coherent And repel water outlet, while keeping solid contents.

As used in this article, " coherent " material be in the form of substantially unitary existing for material, by many compared with The adhesion of fraction and generate, for example, the elastic solid (Hookean body) block of the rubber generated by many small rubber particles are adhering to each other.

As used in this article, " continuous flow " is the stabilization or perseverance for the fluid for continuously coming from source of supply (such as tank) Fixed stream.It is understood, however, that the temporary interruption (for example, one second or a few minutes) of stream is still considered as continuous flow (for example, working as The supply of various supply holding areas of the switching from tank etc. or middle cutout are to adapt to the technique or equipment of downstream units Maintenance when).

In preferred embodiments, the elastomeric compound that can vulcanize can be related to elastomer latices and silica go it is steady Surely the continuous flow process of the liquid mixture for the dispersion changed produces.Any equipment or device or system all can be used, condition It is that the unit or system can be operated to elastomer latices and be mixed with the liquid of the dispersion of the stabilization removal of silica Object can be combined under continuous flow condition and controlled volume flow, pressure and velocity conditions, be included, but are not limited to Fig. 1 (a), (b) or (c) shown in device or any kind of injector or displacer or be arranged for controlled Volume flow, making the continuous flows of at least two liquid flows under pressure and velocity conditions, group is combined through reaction zone in the reaction region Any other equipment.US20110021664, US6048923, WO2011034589, WO2011034587, Device described in US20140316058 and WO2014110499 (being respectively integrally incorporated by reference herein) can be used for Or it uses instead in methods herein.Furthermore, it is possible to use displacer and injector or siphon pipe (such as water jet injector or steam Those of injecting type siphon pipe) (for example, from Schutte＆Koerting, Trevose, PA are commercially available).

The device may include various charging-tanks, pipeline, valve, instrument and pump to control volume flow, pressure and speed. Further, as shown in the entrance (3) in Fig. 1 (a), (b) and (c), can be used various types and size nozzle or Other port size control elements (3a) control the speed of silica slurry.The volume size of reaction zone (13) can be chosen so as to carry For the required volume flow of elastomeric compound and fluid.Entrance (11) to reaction zone supply elasticity body latex can be tapered , in order to provide different rate of volume flow or speed.Equipment may include the entrance (11) of uniform diameter, towards reaction zone Aperture at without any taper.

In the method, by including elastomer latices fluid and include for example as under stress jet stream supply silicon The additional fluid of the dispersion of the stabilization removal of stone is under the conditions of continuous flow and under selected volume flow rate, pressure and speed It combines, to make two fluids quickly and closely mix.The combination (such as under stress in hemi-closure space) So that silica is distributed in entire elastomer latices, also, parallelly, elastomer latices are transformed into solid-state or semisolid from liquid Phase, that is, latex occurs liquid and arrives the reversion or cohesion of solid, to capture the silica and water of distribution in rubber, and anti- Answer the continuous rubber phase for forming the silica containing solid-state or semisolid outside area in the form of continuously or semi-continuously flowing (for example, coming from Fig. 1 (a) opening at bottom (7) in-(c)).At this point, the product can be considered as the elasticity of the continuous rubber phase containing silica granule Nanocrystal composition, the coherent rubber containing silica or silica elastomeric compound.It is believed that silica granule must be distributed across elasticity first To obtain desired product in body latex, also, when silica is distributed, immediately along with liquid to solid phase reversal.However, with Continuous and extremely rapid rate combinations fluid is (that is, being less than 2 seconds, being less than 1 second, be less than 0.5 second, being less than 0.25 second, be less than 0.1 Second or about several milliseconds), also, strong in the reaction region and closely mixing relatively smaller volume fluid (for example, about 10~ The fluid volume of 500cc), the parallel step that the distribution of silica granule changes with the liquid of elastomer latices to solid phase can be almost Occur simultaneously.As used in this article, " reaction zone " is the region for wherein occurring closely to mix along with the cohesion of mixture. Mixture movement is by reaction zone and leads to outlet (7).

Be used to prepare the elastomeric compound that can vulcanize illustrative methods be related to will include silica stabilization removal The first fluid of dispersion and second fluid comprising elastomer latices (such as natural rubber latex) fluid are supplied simultaneously to anti- Answer area.Including the first fluid of the dispersion of the stabilization removal of silica can be supplied with the flow rate based on its volume, and Including the second fluid of elastomer latices can be supplied with the flow rate for being based on its volume (i.e. rate of volume flow).It is first-class The volume flow of both body, second fluid or first fluid and second fluid can be adjusted or provide, so as to generated bullet The silica content of elastomer composite be every 15~180 parts of 100 weight rubber (phr) (such as 35~180phr, 20phr~ 150phr, 25phr~125phr, 25phr~100phr, 35~115phr or 40phr~115phr or 40phr~90phr Deng).Herein, in some embodiments, including the fluid of the dispersion of the stabilization removal of silica be referred to alternatively as it is first-class Body.The fluid is the individual fluid relative to the fluid comprising elastomer latices.Any fluid can by an entrance or Decanting point is introduced by more than one entrance or decanting point.

The volume flow of first fluid (silica dispersion of stabilization removal) and second fluid (latex fluids) can be adjusted Than to allow to be formed desired elastomeric compound.The example of such volume flow ratio includes, but are not limited to 0.4:1 (first fluid is to second fluid)~3.2:1、0.2:1~2:1 equal volume ratio.Volume between first fluid and second fluid Flow-rate ratio can be adjusted by any means or technology.For example, the volume flow of first or second fluid or the two is fast Rate can be adjusted in the following manner：A) rate of volume flow is improved；B) rate of volume flow is reduced；And/or c) adjustment is flowed The flow rate of body relative to each other.The pressure generated by physical constraint is applied on the stream of first fluid results in height Rapid fire stream enables the silica dispersion of stabilization removal and the combination of elastomer latices quickly to occur, for example, several points it In one second.As example, time during two fluid hybrid concurrency life liquid are inverted to solid phase can be about a few millis Second (for example, about 50ms~about 1500ms or about 100ms~about 1000ms).Given selection for fluid, if first The speed of fluid is too slow so that fluid cannot be sufficiently mixed, alternatively, the residence time is too short, then solid rubber phase and solid product Stream may not generate.If the duration of technique is long, back pressure and the continuous flow of material may be generated in the reaction region Stop.Equally, if the duration of first fluid excessive velocities and technique is too short, solid rubber phase and solid product stream can It can not will produce.

As previously mentioned, the opposite bank of first fluid (silica slurry of stabilization removal) and second fluid (latex) can be adjusted Product flow, also, when using at least one salt as destabilizing agent, preferably adjust the silica slurry and elastomer of stabilization removal The volume flow ratio of latex so that it is 0.4:1~3.2:1.Other flow-rate ratios can be used.

When using at least one acid as destabilizing agent, the silica slurry and elastomer latices of stabilization removal are preferably adjusted Volume flow ratio so that it is 0.2:1~2:1.Other flow-rate ratios can be used.

Elastomer latices can contain at least one alkali (such as ammonia), and it is possible to come as addition at least one is sour real The dispersion of the stabilization removal of existing silica, wherein acid in first fluid (silica) in second fluid (latex) alkali (such as Ammonia) molar ratio be at least 1.0 or at least 1.1 or at least 1.2, for example, 1~2 or 1.5~4.5.Alkali can be with each Kind amount is present in elastomer latices, such as, but not limited to, the 0.3wt%~about 0.7wt% (gross weights based on elastomer latices Amount), alternatively, below or above other amounts of the range.

The silica dispersion of stabilization removal can be supplied to reaction zone, it is preferable that the continuous high speed as injection fluid Degree (for example, about 6m/s~about 250m/s or about 30m/s~about 200m/s or about 10m/s~about 150m/s or about 6m/s~about Jet stream 200m/s), moreover, can by the fluid containing elastomer latices at relatively lower speeds (for example, about 0.4m/s~about 11m/s or about 0.4m/s~about 5m/s or about 1.9m/s~about 11m/s or about 1m/s~about 10m/s or about 1m/s~about 5m/s) supplied.Select fluid speed between fluid mixing and elastomer latices quickly agglomerate into Row optimization.Supply to reaction zone elastomer latices speed should preferably high enough to generate turbulent flow so as to stabilization removal Silica slurry be better mixed.However, the speed of elastomer latices should keep sufficiently low so that latex with stabilization removal Silica slurry be sufficiently mixed before will not be agglomerated due to shearing.In addition, before entering reaction zone, elastomer latices Speed should keep sufficiently low, to prevent the emulsion condensation caused by high shear from blocking latex supply line.Similarly, it goes to stablize The range that the speed of the silica dispersion of change optimizes there is also one.It is assumed that if the speed of the silica slurry of stabilization removal It is too high, then may be too high by the rate of the aggregation of the shear-induced of silica granule, so that not allowing silica granule and elastomer Full and uniform mixing between latex particle.

Shear thickening caused by aggregation and networking due to silica granule can also reduce the silica slurry of stabilization removal Turbulent flow and negatively affect the mixing between silica and latex.On the other hand, if the speed of the silica slurry of stabilization removal Degree is too low, then the mixing between silica granule and elastomer latices particle may be insufficient.Preferably, into the fluid of reaction zone At least one of have turbulent flow.Generally, due to typical stabilization removal silica dispersion relative to typical elastomer precursor gum The much higher viscosity of breast is used for and elastomer so needing the much higher speed of the silica dispersion of stabilization removal to generate Latex mixes and the good fluid dynamics of latex quickly agglomerated.Such high velocity stream of the silica dispersion of stabilization removal It is dynamic to cause hole in the reaction region, to enhance point of the quick mixing and silica granule of fluid in elastomer latices Cloth.The speed of the silica dispersion of stabilization removal can be by using different rates of volume flow or the confession at entrance (3a) It is carried out to the different nozzles or tip (diameter is wider or narrower) of the first fluid of the silica dispersion comprising stabilization removal Change.The speed of the silica dispersion of stabilization removal is improved using nozzle, can be provided under following pressures：About 30psi ~about 3,000psi or about 30psi~about 200psi or about 200psi~about 3,000psi or about 500psi~about 2, 000psi, alternatively, being applied at least 2 times of the pressure of the fluid containing elastomer latices or 2-100 times of relative pressure.As reality Example, can provide the second fluid of elastomer latices under the pressure of about 20psi~about 30psi.In first fluid feed system Pressure can be up to about 500psi.

Based on manufacturing variables as described herein (for example, the speed of the silica slurry fluid of stabilization removal, the speed of latex fluids Degree, the relative flow rates of the silica slurry of stabilization removal and latex fluids, destabilizing agent (such as salt and/or acid) concentration, The rubber weight percentage in silica concentration, latex in the slurry of stabilization removal, the ammonia density in latex, and/or acid (if In the presence of if) with the ratio of ammonia), can control, obtain and/or predict the continuous rubber phase of the silica containing solid-state or semisolid in institute Formation within the scope of desired silica content.Therefore, which can run in the range of variables of optimization.Therefore, a) a kind of Or the speed of two kinds of fluids, b) the volume flow ratio of fluid, c) the stabilization removal property of silica, d) stabilization removal silica point The dry rubber content (such as 10~70wt%) of the particle shape silica concentration (such as 6~35wt%) of granular media and e) latex can be permitted Perhaps mixing under the conditions of HI high impact, to cause the liquid of elastomer latices to solid reversion and with selected silica pair Silica is dispersed in latex by the ratio of rubber, to the stream of the continuous rubber phase of formation silica containing solid-state or semisolid. Collecting for the stream of the continuous rubber phase of the silica containing solid-state or semisolid can be with any for collecting solid-state or semisolid material stream Routine techniques realize.This, which is collected, can allow the stream of solid-state or semisolid to enter container or tank or other storage devices.This The container or storage tank of sample may be containing salt or acid or the two solution so that product is further condensed into more elastic shape State.For example, collecting can convey efflux of solids or be pumped into other processing regions or equipment for being further processed, herein In describe some of which selection.Collecting can be continuous, is semi-continuous or in batches.The outflow end of reaction zone is preferably It is semi-enclosed and to atmosphere opening, also, the stream of the elastomeric compound of solid-state or semisolid preferably under ambient pressure into Row is collected to allow the continuous operation of the technique.

The stream of the continuous rubber phase of the silica containing solid-state can be the rope form " worm " of more or less elasticity or the form of bead. In one embodiment, the continuous rubber phase of the silica containing solid-state has following elongation at break, alternatively, it is with following disconnected Split the product of elongation：At least about 100%, for example, about 100%~about 600%, about 120%~about 200%, about 130%~about 150%, about 130%~about 250%, about 150%~about 200%, about 200%~about 300%, about 300%~about 600%, about 300%~about 500% or about 300%~about 400%.In other cases, the continuous rubber phase of the silica containing semisolid can be in The form of non-resilient, viscous paste or gel-like material, can generate elasticity.At each occurrence, output is to connect The flow solids passed through, its consistency (consistency) can be high flexibility or slightly elasticity and it is viscous.Carry out autoreaction The output in area can be substantially invariable stream, point with the stabilization removal of the elastomer latices and silica fluid that enter in reaction zone The ongoing charging of granular media is carried out at the same time.Step (such as preparation of fluid) in the technique can be used as it is continuous, partly connect Continuous or operation in batches is completed.The continuous rubber phase of the silica containing solid-state or semisolid of gained can be subjected to subsequent further Procedure of processing, including, continuous, semicontinuous or operation in batches.

The continuous rubber phase of the silica containing solid-state or semisolid generated in the technique include water or other aqueous fluids and Solute from original fluid, moreover, for example, can include about the water or 40wt%~about 90wt% of 40wt%~about 95wt% Water or the water of about 45wt%~about 90wt% or the water content or about 60~about 80wt% of about 50~about 85wt% Water, the total weight of the stream based on silica elastomeric compound.Alternatively, being formed comprising such water content containing solid-state or After the rubber phase of semisolid silica, dehydration appropriate and plasticate step and blending step can be carried out to the product to generate Required rubber performance simultaneously manufactures Rubber compound.The process and the further details of other post-processing steps are explained below simultaneously And it can be used for producing the elastomeric compound that can vulcanize of any embodiment according to the present invention.

The continuous rubber phase of the silica containing semisolid can be converted into the continuous rubber phase of the silica containing solid-state.This can for example lead to Cross following completion：The continuous rubber phase of the silica containing semisolid is set to undergo the mechanical step for removing water from compound and/or make partly Solid-state material stands such as 10 minutes to 24 hours or longer time (for example, being received in the reaction zone from positioned at offline position After taking)；And/or the continuous rubber phase of heating silica containing semisolid is to remove water content (for example, about 50 DEG C~about 200 DEG C Temperature)；And/or make semi-solid material experience acid or additional acid (such as in acid bath) or experience salt or additional salt or The combination of salt bath or experience acid and salt；Etc..One or more of these steps or whole can be used.In fact, i.e. Make in the continuous rubber phase for initially or subsequently collecting the silica containing solid-state, one or more or Overall Steps are still used as into one The processing step of step.The fracture of the continuous rubber phase of the silica containing solid-state of gained or the continuous rubber phase product of the silica containing solid-state is stretched Long rate can be at least about 100%, for example, about 100%~about 600%, about 130%~about 150%, about 120%~about 200%, About 200%~about 500%, about 300%~about 400%, about 150%~about 200% or about 130%~about 250%.

The stabilization removal degree of silica slurry determine at least partly in silica slurry given silica concentration and The given dry rubber content of latex may be present in silica elastomeric compound (for example, capturing and being evenly distributed on compound In object) silica amount.In ratio relatively low (for example, 15phr~45phr) of selected target silica and rubber, go to stablize The concentration of agent may not be sufficiently high in silica slurry, also, finally, be insufficient to allow the fast rapid hardening of silica/latex mixture Coalescence forms the continuous rubber phase of the silica containing solid-state or semisolid.In addition, selecting suitable silica and rubber as described herein Concentration and fluid relative flow rate appropriate are factors the considerations of forming solid-state or semisolid product.For example, in stabilization removal Slurry/latex volume flow ratio it is relatively low when, the amount of the destabilizing agent in the silica slurry of stabilization removal may be insufficient To promote elastomer latices in the quick cohesion of reaction zone.It, can be by improving silicon generally, for given elastomer latices The stabilization removal of stone slurry and/or the weight percent of silica in the slurry of stabilization removal is reduced to realize lower silica load Amount.

When the dispersion stabilization removal of silica, silica granule is intended to flocculate.When the dispersion too height of silica When stabilization removal, silica can be from " falling " in solution and become unsuitable for in preferred embodiment.

When stabilization removal occurs, the surface charge on silica will not be typically completely removed.However, sometimes, working as silicon When stone particle or silica dispersion are treated as stabilization removal, isoelectric point (IEP) may cross positive ζ electricity from negative zeta potential Gesture value.For silica, the net charge on the surface of silica granule is reduced, also, during stabilization removal, ζ electricity The magnitude of gesture reduces.

For the ratio of higher silica and rubber in silica elastomeric compound, the slurry of stabilization removal can be selected In higher silica concentration and/or higher silica fluid and latex fluids volume flow ratio.Once silica slurry is gone It stabilizes and starts to combine with latex fluids, if mixture is non-condensing, first fluid and second fluid can be adjusted Volume flow ratio, such as the volume flow by reducing latex, this effectively provides the higher silicon in elastomeric compound Stone/rubber ratio.In the step for adjusting latex amount, the amount of latex is or becomes destabilizing agent will not be made entire The amount of concentration excess dilution in mixture so that required product can be formed within the residence time in the reaction region.In order to The ratio of required silica and rubber is obtained in elastomeric compound, there can be various selections.It is selected as one, Ke Yizeng Add the stabilization removal of silica slurry horizontal, such as the magnitude by reducing the zeta potential of the silica slurry of stabilization removal (such as passes through More salt and/or acid is added).Alternatively, as a kind of selection, the silica that can be adjusted in the silica slurry of stabilization removal is dense It spends, such as the silica concentration in the silica slurry by reducing or increasing stabilization removal.Alternatively, as a kind of selection, can make With the latex with higher rubber content, alternatively, latex can be diluted to lower rubber content, alternatively, glue can be improved The relative flow rates of breast.Alternatively, as a kind of selection, thus it is possible to vary flow rate and port size (wherein can respectively be controlled System or influence fluid speed) or two fluid streams relative direction, stopped in reaction zone with shortening or extending composite fluid Stay the amount and type of the turbulent flow at time and/or the shock point of change first fluid and second fluid.These selections can be used Any one of or two or more carry out adjusting process parameter and obtain the target in elastomeric compound or required silicon The ratio of stone and rubber.

The amount or degree of the stabilization removal of silica slurry are to determine the ratio of silica and rubber in silica elastomeric compound The principal element of rate.When the silica slurry of stabilization removal mixes in the reaction region with elastomer latices, for making in slurry The destabilizing agent of silica stabilization removal may be to promoting the cohesion of elastomer latices particle to work.It is assumed that in reaction zone The rate of emulsion condensation is likely to be dependent on the concentration of the destabilizing agent in composite fluid.It has been observed that by various conditions Lower operation method for being used to produce silica elastomeric compound, it may be determined that in mixing in the combined mixture of fluid In the presence of destabilizing agent threshold concentration, effectively generate the continuous rubber phase of the silica containing solid-state or semisolid.Under Selection is described in the embodiment in face and adjusts process conditions to realize threshold concentration to generate silica containing solid-state or semisolid Continuous rubber phase example.If threshold concentration relative to given selection and fluid composition, volume flow and speed not Match or be more than, then not will produce the continuous rubber phase of the silica containing solid-state or semisolid usually.

The minimum of the stabilization removal of silica slurry is by the zeta potential magnitude less than 30mV (such as with such as -29.9mV~about 29.9mV, about -28mV~about 20mV, about -27mV~about 10mV, about -27mV~about 0mV, about -25mV~about 0mV, about -20mV The zeta potential of~about 0mV, about -15mV~about 0mV, about -10mV~about 0mV etc.) instruction.If silica slurry is gone to stablize Change into the zeta potential, then it can be by stabilization removal when the silica in the slurry of stabilization removal is combined with elastomer latices Slurry in silica be attached in the continuous rubber phase of the silica containing solid-state or semisolid.

Although may want to make latex stabilization removal before latex is combined with silica slurry, in a shear condition (example Those of as present in when latex is continuously pumped into reaction zone under shearing condition), it is difficult to make latex fluids go to stablize in advance The too early cohesion changed without causing latex.However, the destabilizing agent used in the silica slurry of stabilization removal may be with excess quantity In the presence of to enhance the stabilization removal of latex, and/or, mitigate the reagent when the silica slurry of stabilization removal and latex fluids combine Dilution.As a further alternative, in extra high silica concentration (for example, in silica slurry>25wt% silicas) when, it can The silica slurry and elastomer latices of the stabilization removal in reaction zone are added separately to the destabilizing agent for being added some Mixture in enhance the cohesion of latex.

Be not intended to be limited to any theory, it is believed that this be used to produce the method for silica elastomeric compound with about two seconds or The coherent interpenetrating networks that the shorter time (such as part second) forms rubber grain and silica aggregation, due to occurring two The combination and phase reversal of a fluid lead to the material of the solid-state or semisolid comprising these networks with packaged water.It is such Fast network forms continuously generating for the continuous rubber phase for allowing the silica containing solid-state or semisolid.It is assumed that with stabilization removal Silica slurry combine with elastomer latices by inlet nozzle, the shear-induced of silica granule, which is assembled, can be used in rubber Unique and uniform particle arrangement is generated in glue masterbatch and is captured in rubber by the heterocoagulation between silica and rubber grain Silica granule.Further speculate, in the case of not such interpenetrating networks, following solid-state or partly solid may be not present The continuous rubber phase compound of state：It includes the silica granules of the dispersion in worm or solid plate shape, for example, it is packaged with The water of 40-95wt% and keep all or most of in subsequent dehydration (including squeeze and high energy mechanical processing) Silica.

It is assumed that with the silica slurry of stabilization removal with high speed via first entrance (3) by pressurized nozzles (3a) into Enter reaction zone (13) (as shown in Figure 1), the formation of silica network is at least partially from the silica granule aggregation of shear-induced.When Silica slurry is when (for example, by handling silica slurry with salt or acid or the two) becomes stabilization removal, the process due to The stability of silica in the slurry of stabilization removal is reduced and is become easy.

It is assumed that the liquid of latex may be caused to solid phase reversal by many factors, include by the silicon with stabilization removal Shear-induced cohesion caused by the mixing of the high-speed jet of stone slurry, the interaction of silica surface and latex component, from The ion of the contact of silica slurry containing destabilizing agent or chemical coagulation and the combination of these factors.Include to be formed The composite material of interpenetrating silica network and rubber network should balance the rate of each network formation and mixed rate.Example Such as, for the silica slurry of the height stabilization removal in slurry under high salt concentration, the aggregation of silica granule and network Form rapid in a shear condition occur.In this case, it is quick to be set so that latex has for volume flow and speed Cohesion rate is to form silica/rubber network of interpenetrating.Using the silica slurry of slighter stabilization removal, then the rate formed is got over Slowly.

Manufacture silica elastomeric compound an illustrative methods include by entrance 11 (Fig. 1 (a), (b), and/or (c)) with the rate of volume flow of about 20L/hr~about 1900L/hr by the fluid (sometimes referred to as the containing at least elastomer latices Two fluids) continuous flow supply to reaction zone 13.This method further comprises by nozzle tip (capable of in Fig. 1, being located at At 3a) it is steady by the supply of entrance 3 going comprising silica with the rate of volume flow of 30L/hr~1700L/hr under the pressure that reaches Surely the continuous flow of another fluid (sometimes referred to as first fluid) for the dispersion changed.The stabilization removal state of silica dispersion and Under the high energy conditions generated by introducing the first fluid as high-speed jet (for example, about 6m/s~about 250m/s) The collision of (being introduced at entrance 3 and 11) two fluid streams so that the silica is closely mixed with latex stream, promote Silica in the stream of the continuous rubber phase of the silica containing solid-state from reaction zone exit is uniformly distributed, wherein this is first-class The high-speed jet of body is with the latex stream for the relatively low velocity for entering reaction zone with the angle substantially vertical with it (for example, 0.4-11m/ S) it collides.

Alternatively, the elastomer latices introduced for example, by entrance 11 can be the blending of two or more latex Object, for example, two or more synthetic latexes blend.Alternatively, Fig. 1 (a), (b) and/or (c) in equipment can be changed Become with one or more additional entrances, to introduce other components, such as one or more additional glue to reaction zone Breast.For example, in Fig. 1 (c), other than using entrance 11, entrance 14 also can be used to introduce further latex.One or more A additional entrance can be follow one another, can also be adjacent to each other or be arranged in any direction, as long as being drawn by entrance There is the material (such as latex) entered time enough to be disperseed or be incorporated into the stream of gained.In WO2011/034587 In (which is hereby incorporated by reference for it), Fig. 1,2A and 2B provide the example in additional entrance and its direction, these can be with Herein using for the production elastomeric compound according to embodiments of the present invention that can vulcanize.As specific example, One entrance can introduce the stream comprising natural rubber latex, also, other entrance can introduce the elastomer latices of synthesis, And these latex streams are combined with the stream of the dispersion of the stabilization removal of silica to lead to the continuous of the silica containing solid-state or semisolid The stream of rubber phase.When the entrance more than one is used for the introducing of elastomer latices, flow rate can be mutually the same or not Together.

Fig. 2 illustrates an example using the block diagram for the various steps that may occur in elastomeric compound forming process. As shown in Figure 2, the dispersion (first fluid) 100 of the stabilization removal of silica is introduced into reaction zone 103, and will will include elasticity The fluid (second fluid) 105 of body latex is also introduced into reaction zone 103.Alternatively, the continuous rubber of the silica containing solid-state or semisolid The stream of glue phase leaves reaction zone 103 and can optionally enter memory block 116 (for example, storage tank, adds or be not added with salt or acid is molten Liquid is to further enhance the cohesion of rubber and the formation of silica/rubber network)；Furthermore, it is possible to optionally directly or be transferred to Enter drying zone 105 after memory block 116；Continuous mixer/blender 107 can be optionally entered；It can optionally enter Grinding machine (for example, open mill, also referred to as roller mill) 109；It is (identical as grinding machine 109 or not can be subjected to additional additional grinding 111 Same condition) (such as identical or different energy input)；It can be by mixing machine 115 into the mixing of line option；And/or it can be with Using comminutor 117 be granulated and be then optionally packaged using baling press 119, and can be optionally by making It is cracked with additional mixing machine 121.

About silica, the silica of one or more types or silica can be used in any embodiment of the present invention Any combinations.The feature of silica suitable for enhancing elastomeric compound can be following surface area (BET)：About 20m²/ g~about 450m²/g；About 120~about 225m²/g；About 30m²/ g~about 450m²/g；About 30m²/ g~about 400m²/g；Alternatively, about 60m²/g ~about 250m²/g；Moreover, for heavy vehicle tyre tyre surface, BET surface area is about 60m²/ g~about 250m²/ g, alternatively, For example, about 80m²/ g~about 200m²/g.The precipitated silica for capableing of high degree of dispersion can be used as filler in the method for the present invention.It can be high The precipitated silica (" HDS ") of degree dispersion is understood to refer to have de-agglomerated and the basic capacity that is dispersed in elastomeric matrices Any silica.This judgement can be by electronics or light microscope in known manner on the slice of elastomeric compound It observes.The example of the HDS of class of trade includes：From WR Grace＆Co'sGT 3000GRAN silicas come From Evonik Industries'7000 silicas, from Solvay S.A.'s1165MP and 1115MP silicas, the Hi- for coming from PPG Industries, Inc.EZ 160G silicas and come from JM Huber Corporation's8741 or 8745 silicas.Conventional non-HDS precipitated silicas can also be used.Class of trade it is normal Rule precipitated silica example include：From WR Grace＆Co's408 silicas of KS, from Solvay S.A.'s175GR silicas, from Evonik Industries'VN3 silicas come from PPG Industries, Inc. Hi-243 silicas and from JM Huber Corporation's161 silicas.It can also The hydrophobic precipitated silica of silane coupling agent is connected with using surface.The example of the hydrophobic precipitated silica of class of trade includes： From PPG Industries, Inc.'s400,454 or 458 silicas and from Evonik Industries' Coupsil silicas, such as 6109 silicas of Coupsil.

Typically, the silica content of silica (such as silica granule) is at least 20wt%, at least 25wt%, at least 30wt%, at least 35wt%, at least 40wt%, at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt% or almost 100wt% or 100wt% or about 20wt%~about 100wt%, are all based on the total weight of particle. Any silica can be chemically functionalized, such as the chemical group with connection or absorption is (such as the organic group for connecting or adsorbing Group).Any combinations of silica can be used.The silica for forming silica slurry and/or the silica slurry of stabilization removal can part Or be entirely the silica with hydrophobic surface, it can be hydrophobic silica or silicon is made by processing (such as chemical treatment) Stone surface hydrophobicity and become that there is hydrophobic silica.Hydrophobic surface can be by with the hydrophobic silane without ionic group (for example, double-triethoxysilylpropyltetrasulfide tetrasulfide) carries out chemical modification to obtain to silica granule.It is such in silicon On stone surface reaction can before dispersion to be carried out in individual processing step, alternatively, in silica dispersion in situ into Row.Surface reaction reduces the silanol density in silica surface, to reduce the ionic charge density of the silica granule in slurry. The suitable silica granule through hydrophobic surface treatments for dispersion can be obtained by commercial source, for example, coming from PPG Industries's454 silicas and400 silicas.The silica of silica dispersion and stabilization removal disperses Body can use the silica granule with low surface silicon alkanol density to be made.Such silica can exist via such as calcine technology It is obtained by dehydroxylation at a temperature of more than 150 DEG C.

In addition, it is alternatively that, the silica slurry of silica slurry and/or stabilization removal can contain small amount and (be based on particle material Expect total weight 10wt% or less) any non-silica granule, such as carbon black or zinc oxide or calcium carbonate or be used for rubber Other particulate materials (for example, carbon black of the precipitated silica of 95wt% and 5wt%) of glue composition.Can select it is any enhancing or The carbon black of non-reinforcing grade in final rubber composition to generate desired performance.

According to any technology well known by persons skilled in the art, silica can be dispersed in aqueous fluids.Particle shape silica Dispersion can be subjected to mechanical treatment for example to reduce granularity.This can before or during dispersion stabilization removal or later It completes, and it is possible in a manner of secondary or main mode makes contributions to the stabilization removal of dispersion.The mechanical treatment can Contain or comprise pulverize, grind, crushing, the processing of impact or high shear fluid or its arbitrary combine.

For example, silica slurry can be by being manufactured with pulverizing technique and disperse silica in a fluid.It is such to pulverize technique Being reduced in size to most of silica aggregate (such as more than 80 volume %) in fluid less than 10 microns and being preferably shorter than 1 micron (typical size range of colloidal solid).Fluid can be water, aqueous fluids or non-aqueous polar fluid.For example, slurry Material can include about the particle (weight based on slurry) containing silica of 6wt%~about 35wt%.The size of silica granule can make It is measured with light scattering technique.When being made in water using with the silica granule of low-residual salt content in the case where pH is 6-8 When standby, such slurry typically has the zeta potential magnitude greater than or equal to 30mV and is being slowly stirred (such as mixing speed Less than 60RPM) under good resistant to aggregation, gelling and the stability of sedimentation are shown in holding vessel.Due to through well grinding Silica granule usually because high negative electrical charge on silica and stablize in water at about 7 pH, it is thus typically necessary to very high Shearing to overcome the repulsion energy barrier between particle to cause particle aggregation.

In the illustrative methods using silica (such as HDS particles), silica can be combined with water, and be made obtained Mixture is by colloid mill, pipeline grinding machine etc. to form dispersion fluid.Then, which is sent into homogenizer, the homogenizing Filler is more subtly dispersed in carrier fluid to form slurry by device.Illustrative homogenizer include, but are not limited to from Microfluidics International Corporation (Newton, Mass., USA) are commercially availableSystem.In addition, such as homogenizer of MS18, MS45 and MC120 type and from APV Homogenizer Division of APV Gaulin, Inc. (Wilmington, Mass., USA) commercially available series of homogenizer device is also suitable 's.Other suitable homogenizers are commercially available, and to those skilled in the art in the benefit of the given disclosure In the case of will be apparent.The optimum operation pressure of homogenizer may depend on actual device, the type of silica and/or silica Content.As example, homogenizer can operate in the following pressure：About 10psi~about 5000psi or higher, for example, about 10psi~about 1000psi, about 1000psi~about 1700psi, about 1700psi~about 2200psi, about 2200psi~about 2700psi, about 2700psi~about 3300psi, about 3300psi~about 3800psi, about 3800psi~about 4300psi or about 4300psi~about 5000psi.As previously mentioned, before carrying out masterbatch technique, the dispersion of particle shape silica is destabilized, And it is any pulverize or similar mechanical process before, during or after, can be with by following one of the technology being mentioned herein Dispersion is set to be destabilized.

Depending on used wet method master batch method, the high silica concentration in slurry can be used for reducing remove extra water or The task of other carriers.For the dispersion of the stabilization removal of silica granule, liquid used can be water or other aqueous Fluid or other fluids.For the dispersion of the stabilization removal, the filler of about 6wt%~about 35wt% can be used, for example, About 6wt%~about 9wt%, about 9wt%~about 12wt%, about 12wt%~about 16wt%, about 10wt%~about 28wt%, about 16wt%~about 20wt%, about 20wt%~about 24wt%, about 24wt%~about 28wt% or about 28wt%~about 30wt%, The weight of dispersion based on stabilization removal.For the dispersion of the stabilization removal, higher silica concentration can have benefit Place.For example, the silica concentration in the slurry of stabilization removal can be at least 10wt% or at least 15wt% (weight based on slurry) (for example, about 12wt%~about 35wt% or about 15.1wt%~about 35wt% or about 20wt%~about 35wt%), this can be with There is provided benefit, such as, but not limited to, the reduction of equipment size needed for the waste water of reduction, the productivity of raising, and/or technique.Mirror In the benefit of the disclosure, it would be recognized by those skilled in the art that silica slurry (and in silica slurry of stabilization removal) Silica concentration (unit wt%) should be coordinated with other state-variables during wet processing, to be reached in final product To the ratio (unit phr) of desired silica and rubber.

The details of the dispersion of silica is described further below.In general, dispersion can comprise more than the material of a phase Material, wherein at least one phase is comprising finely divided phase domain or including finely divided phase domain or by finely divided phase domain It constitutes, optionally within the scope of colloid size, is dispersed in entire continuous phase.The dispersion or slurry or silica of silica are disperseed Body can be produced as stable suspension of the particle shape silica in aqueous fluids, wherein the charge at particle surface prevents Grain aggregation, and dispersion is characterized in that the zeta potential magnitude more than or equal to 30mV.In such dispersion, silica Grain is kept for for example, at least 8 hours relative to assembling and be flocked in stable dispersion and/or suspension.Stable dispersion can To be to maintain the dispersion of constant particle size, and wherein in the presence of slow or periodically stirring, particle does not settle or gel Change or needs the time grown very much just it appear that settling, for example, the nothing behind 8 hours or 12 hours or 24 hours or 48 hours The sedimentation that could see.For example, in order to make colloidal silica particle be well dispersed into aqueous fluids, it usually can be from 8 to 10 PH observes stability.Further, being slowly stirred with dispersion, silica granule is by means of Particle surface charge, particle Surface polarity, pH, selected granule density, particle surface processing and combinations thereof and remain suspended in fluid.Fluid can be with It is or including water, aqueous mixture or miscible with water or partial miscibility fluid, such as various alcohol, ether and other low molecules The solvent miscible with water of amount preferably has C₁-C₅Organic group (for example, ethyl alcohol, methanol, propyl alcohol, ether, acetone etc.).Such as Preceding described, dispersion for example can include about 6wt%~about 35wt%, about 10wt%~about 28wt%, about 12wt%~about The particle containing silica of 25wt% or about 15wt%~about 30wt%, the weight based on dispersion.

Stable dispersion can be aqueous colloidal dispersion.In general, aqueous colloidal dispersion or colloid can be that wherein discrete particles are outstanding Float on the substance in entire another substance.Dispersion particle has substantially about 1 nanometer~about 1000 nanometers and typically about 100 Nanometer~about 500 nanometers of diameter.In stable aqueous colloidal dispersion, granularity, density and concentration make gravity not lead to particle Easily precipitate from dispersion.The magnitude of zeta potential is that the colloid of 30mV or more is typically considered stable colloid System.The reduction of the granule stability (such as silica) for being attributed to charge stability in colloid or dispersion can pass through ζ electricity The reduction of gesture magnitude measures.Granularity can be measured by light scattering method.

The silica dispersion of stabilization removal can be understood as the dispersion of silica in a fluid, wherein the particle-of decrease Grain repulsive force allow particle gathering and silica pellet-pellet network formation or gelling (once the dispersion of stabilization removal By a effective amount of shearing).In some cases, mechanical shearing can lead to the stabilization removal and silica granule of silica dispersion Gathering.The stabilization removal degree of silica slurry is higher, and the shearing force needed for particle aggregation is smaller, and the rate of particle aggregation is got over It is high.For the dispersion of stabilization removal, the particle shape silica that dispersion can include about 6wt%~about 35wt% (is based on dividing The weight of granular media), for example, about 8wt%~about 35wt%, about 10wt%~about 28wt%, about 12wt%~about 25wt%, about 15wt%~about 30wt%.Aqueous fluids in the dispersion of the stabilization removal of silica granule can be or including water, aqueous mixed Close object or miscible with water or partial miscibility fluid, for example, various alcohol, ether and other low molecular weights it is miscible with water molten Agent preferably has C₁-C₅Organic group (for example, ethyl alcohol, methanol, propyl alcohol, ether, acetone etc.).It is multiple in order to form silica elastomer Close object, by before slurry mix with latex using a effective amount of destabilizing agent is such as sour or salt or the two come reduce particle it Between electrostatic barrier, the stability of the silica granule in slurry or dispersion occurs to reduce (that is, stabilization removal).Destabilizing agent can It is chosen so as to reduce the repulsion charge interaction between the particle surface for preventing particle from assembling in a fluid.

It (is about pH for typical hydrophily silica that pH by reducing silica dispersion, which is close to the isoelectric point of silica, 2) dispersion of the stabilization removal of silica can, be obtained.For example, can be by adding acid with by the dispersion of particle shape silica PH is reduced to 2~4 the magnitude of the zeta potential of dispersion is thus decreased to less than 30mV for example, less than about 28mV (for example, for formic acid For destabilizing agent, zeta potential magnitude is about 18mV~about 6mV) obtain the silica of stabilization removal.Add in silica slurry The stability for the silica granule being dispersed in water can effectively be reduced by entering acid and/or salt.The molar concentration of acid or salt is typically certainly Determine the principal element of the zeta potential of the silica slurry of stabilization removal.In general, can using the acid of sufficient amount or salt or the two come by The magnitude of the zeta potential of silica slurry decreases below 30mV (such as 28mV or smaller, preferably 25mV or smaller), contains to generate The continuous rubber phase of semisolid or solid-state silica.

For alloing the amount of the acid of silica dispersion stabilization removal to be to be less than 30mV (such as 28mV or more for obtaining Small or 25mV or smaller) the zeta potential magnitude in the dispersion of stabilization removal amount.Acid can be at least one organic acid Or inorganic acid.Acid can be or including acetic acid, formic acid, citric acid, phosphoric acid or sulfuric acid or its arbitrary combination.Acid can be or Including including C₁-C₄The acid of alkyl.Acid can be or including molecular weight or weight average molecular weight less than 200 (such as less than 100MW or Less than 75MW or about 25MW~about 100MW) acid.The amount of acid can change and depending on just disperseing in the silica of stabilization removal Body.The amount of acid can be, for example, about 0.8wt%~about 7.5wt%, such as about 1.5wt%~about 7.5wt% or higher (are based on Include the total weight of the fluid of silica dispersion).If tartaric acid is the destabilizing agent uniquely used, then sour amount can be such Amount, make the pH of silica dispersion reduce at least two pH units or be down at least 5 or lower pH or used it is a kind of or The pKa ranges of a variety of acid, to reduce the charge interaction between particle.

It is by handling silica dispersion with the destabilizing agent comprising one or more salt that the zeta potential change of slurry is supreme Range is stated, the dispersion of stabilization removal is can get.The salt can be or including at least one metal salt (for example, coming from the 1st, 2 Or 13 race metal).The salt can be or including calcium salt, magnesium salts or aluminium salt.Illustrative counter ion counterionsl gegenions include nitrate anion, Acetate, sulfate radical, halide ion, such as chlorine root, bromine root, iodine root etc..The amount of salt can be, for example, about 0.2wt%~about 2wt% or higher, for example, about 0.5 or 1wt%~about 1.6wt% (fluids of the dispersion based on the stabilization removal comprising silica Weight).

The combination of at least one salt and/or at least one acid can be used for making the dispersion stabilization removal of silica.

When by adding dispersion of at least one salt to obtain the stabilization removal of silica, point of the stabilization removal of silica Salinity in granular media can be about 10mM~about 160mM or other amounts higher or lower than the range.

When by adding dispersion of at least one acid to obtain the stabilization removal of silica, the dispersion of the stabilization removal In acid concentration can be about 200mM~about 1000mM (for example, about 340mM~about 1000mM) or be higher or lower than the model The other amounts enclosed.

The silica dispersion of stabilization removal can be made of silica granule, which is handled to be taken comprising suitable Positively charged surface functional group, to make the net charge in silica surface be sufficiently reduced zeta potential to reduce dispersion Magnitude is to less than 30mV.Due to such surface treatment, the net charge in silica surface can be positive, rather than negative.Band The functional group of positive charge can be by being connected chemically or physical absorption by is introduced to silica surface.For example, silica surface can made It is handled with N- trimethoxy-silylpropyls-N, N, N- trimethyl ammonium chloride before or after standby silica dispersion.It can also The Liquidity limit type smears in silica surface, for example, amine-containing molecule and basic amino acid.It is assumed that silica granule table Net positive charge on face can enhance the cohesion of the latex comprising negatively charged rubber grain by heterocoagulation.

About " second fluid " containing at least one elastomer latices, which can contain one or more elastomer precursor gums Breast.Elastomer latices are considered the aqueous colloidal dispersion of the stabilization of rubber, and can contain, for example, based on latex The rubber of the about 10wt% of total weight~about 70wt%.For example, rubber can be dispersed in fluid (such as water or other aqueous flows Body) in.The aqueous materials content (or water content) of the fluid can be 40wt% or higher, for example, 50wt% or higher or 60wt% or higher or 70wt% or higher, for example, about 40wt%~90wt% include at least one elastomer latices based on being somebody's turn to do Fluid weight.Suitable elastomer latices include natural and synthetic elastomer latex and latex blends.For example, elastomer Latex can be synthetically prepared with the monomer of surfactant emulsifies such as styrene by polymerization.Latex should be suitble to selected The expected purpose or application of wet method masterbatch technique and final rubber product.It below will be in the limit of power of those skilled in the art It is interior：In view of the benefit of the disclosure, select suitable elastomer latices or suitable elastomer latices blend for herein In the methods and apparatus disclosed.

Elastomer latices can be or include the lotion of natural rubber, such as natural rubber.Illustrative natural rubber latex Breast include, but are not limited to fresh latex, latex concentration object (for example, being generated by evaporation, centrifugation or emulsification), glue it is clear (for example, By centrifuging the remaining supernatant after generating latex concentration object) and any two in these or more is in any proportion Blend.Natural rubber latex is typically with ammonia treatment to protect it, also, the pH of processed latex is typically In the range of 9~11.The ammonia content of natural rubber latex can be adjusted, and can be reduced, for example, by making nitrogen be bubbled Across or through latex.Typically, latex supplier makes latex remove sludge by adding Diammonium phosphate (DAP).They can also lead to Addition ammonium laurate is crossed to make latex stablize.Natural rubber latex can be diluted to required dry rubber content (DRC).Therefore, The latex that can be used herein can be the latex through slagging-off.Can also include auxiliary anticorrosion agent, tetramethylthiuram disulfide With the mixture (TZ solution) of zinc oxide.Latex should be suitble to the expected purpose of selected wet method masterbatch technique and final rubber product Or application.Latex is typically provided in water carrier fluid (such as water).The amount of aqueous carrier solution can change, for example, aboutWeight based on fluid.The amount of water carrier fluid is alterable, and for example, about 30wt%~about 90wt% (weight based on fluid).In other words, such natural rubber latex may include or can be adjusted to that include example Such as, the rubber of about 10wt%~about 70wt%.Know in view of universally recognized selection criteria in the benefit and industry of the disclosure Know, selects the blend of suitable latex or latex will be completely in the limit of power of those skilled in the art.

Natural rubber latex may also carry out chemical modification in some manner.For example, it can be handled, to chemistry Or the mode of enzyme is modified or restores various non-rubber components, alternatively, various monomers or other chemistry can be used in rubber molecule itself Group such as chlorine is modified.Epoxidized natural rubber latex can be it is particularly advantageous that because epoxidized rubber quilt Think with silica surface interaction (Martin etc., Rubber Chemistry and Technology, in May, 2015, doi:10.5254/rct15.85940).The illustrative methods description of chemical modification is carried out in following to natural rubber latex： European Patent Publication No.1489102,1816144 and 1834980；Japanese Patent Publication No.2006152211,2006152212, 2006169483,2006183036,2006213878,2006213879,2007154089 and 2007154095；British patent No.GB2113692；United States Patent (USP) No.6,841,606 and 7,312,271；And U.S. Patent Publication No.2005-0148723. Other methods well known by persons skilled in the art can also be used.

Other examples elastomer includes, but are not limited to：Rubber；1,3- butadiene, styrene, isoprene, isobutene, 2,3- dialkyl group -1,3-butadiene (wherein, alkyl can be methyl, ethyl, propyl etc.), acrylonitrile, ethylene, propylene etc. gather Close object (such as homopolymer, copolymer and/or terpolymer).It is measured by differential scanning calorimetry (DSC), elastomer can have There is about -120 DEG C~about 0 DEG C of glass transition temperature (Tg).Example includes, but are not limited to SBR styrene butadiene rubbers (SBR), natural rubber and its derivative such as chlorinated rubber, polybutadiene, polyisoprene, poly- (styrene-co-butadiene) with And the derivative through oily increment of any one in them.Any blend of aforementioned substances can also be used.Latex can be aqueous In carrier fluid.Specially suitable synthetic rubber includes：The copolymer of styrene and butadiene, it includes about 10wt%~about 70wt% Styrene and about 90~about 30wt% butadiene, for example, the copolymer of 19 parts of styrene and 81 parts of butadiene, 30 parts of benzene second The copolymer of alkene and 70 parts of butadiene, the copolymer of 43 parts of styrene and 57 parts of butadiene and 50 parts of styrene and 50 parts of fourths two The copolymer of alkene；The polymer and copolymer of conjugated diene such as polybutadiene, polyisoprene, polychlorobutadiene etc. and this The conjugated diene of sample with being capable of monomer (such as styrene, methyl styrene, chlorostyrene, third copolymerized therewith containing ethylenic group Alkene nitrile, 2- vinyl-pyridins, 5- methyl -2- vinylpyridines, 5- ethyl -2- vinylpyridines, 2- methyl -5- vinylpyridines Pyridine, through allyl substitution acrylate, vinyl ketone, methyl isopropenyl ketone, methyl vinyl ether, alpha-methylene carboxylic acid with And its ester and amide such as acrylic acid and dialkyl group acrylic acid amides) copolymer.Ethylene and other high alhpa olefins such as propylene, 1- fourths The copolymer of alkene and 1- amylenes is also applicable in herein.The blend of two or more elastomer latices can also be used, including is closed At with natural rubber latex blend or with two or more synthesis or natural rubber.

Other than elastomer and filler and coupling agent, the elastomeric compound that can vulcanize can also contain various processing Auxiliary agent, extending oil, antidegradant, antioxidant and/or other additives.

The amount (unit is the rubber of part/100 or phr) of silica in the presence of elastomeric compound can be about 15phr~about 180phr, about 20phr~about 150phr, about 25phr~about 80phr, about 35phr~about 115phr, about 35phr~about 100phr, about 40phr~about 100phr, about 40phr~about 90phr, about 40phr~about 80phr, about 29phr~about 175phr, About 40phr~about 110phr, about 50phr~about 175phr, about 60phr~about 175phr etc..Elastomer through silica enhancing is multiple Close object optionally and include a small amount of carbon black for color, electric conductivity and/or UV stability and/or for other purposes.Elasticity Few amount of carbon black contained in nanocrystal composition can be, for example, about 0.1wt%~about 10wt%, based in elastomeric compound The weight of existing whole particles.The carbon black of any grade or type can be used, for example, enhancing or half enhancing tire grade stove Method carbon black etc..

In any method for the elastomeric compound that production can vulcanize, in the company for forming the silica containing solid-state or semisolid After continuous rubber phase, the method can also include one or more following steps：

One or more storing steps or further solidification or agglomeration step are to generate further elasticity；

One or more dehydrations can be used for making compound dehydration to obtain the compound through dehydration；

One or more extrusion steps；

One or more calendaring processes；

One or more grinding steps are to obtain ground compound；

One or more granulation steps；

One or more is packaged step to obtain the product or mixture through packing；

Mixture or product through packing can be separated to form the mixture through granulation；

One or more mixing or blending step are to obtain the compound through compounding.

It can occur such as after the continuous rubber phase for forming the silica containing solid-state or semisolid as further example The step of lower sequence, and each step can repeat arbitrary number of times (having identical or different setting)：

One or more storing steps or further agglomeration step are to generate further elasticity

Make compound (for example, leaving the elastomeric compound of reaction zone) dehydration to obtain the compound through dehydration；

Compound through dehydration is mixed or is compounded to obtain the mixture through compounding；

The mixture through compounding is ground to obtain ground mixture (for example, roller mill)；

To this, ground mixture is granulated or is mixed；

Optionally, after granulation or mixing, mixture is packaged to obtain the mixture through packing；

Optionally, it separates the mixture through packing and is mixed.

In any embodiment, coupling agent (or in multiple steps or position) can introduce in any step, only Coupling agent is wanted to have an opportunity to become to be dispersed in elastomeric compound.

As one example only, the continuous rubber phase for leaving the silica containing solid-state or semisolid of reaction zone or conversion zone can It is transferred in dewatering extruder by suitable device (such as band or conveyer belt).Suitable dewatering extruder is well known and can It is commercially available from such as French Oil Mill Machinery Co. (Piqua, Ohio, USA).Selectively or this Outside, the continuous rubber phase of the silica containing solid-state or semisolid can for example be compressed between metallic plate, aqueous fluids phase is discharged At least part, for example, discharge aqueous fluids until such material water content be less than 40wt%.

In general, post-processing step may include elasticity of compression nanocrystal composition to remove about 1wt%~about 15wt% or higher Aqueous fluids phase (total weight based on elastomeric compound).Dewatering extruder may make silica elastomeric compound from for example greatly About 40%~about 95% water content is caused to reach substantially about 5%~about 60% water content (for example, about 5%~about 10% water Content, about 10%~about 20% water content, about 15%~about 30% water content or about 30%~about 50% water content), Wherein, all wt% are all based on the total weight of compound.Dewatering extruder can be used for containing in the water of silica elastomeric compound Amount is down to about 35wt% or other amounts.Best water content can with elastomer used, the amount of filler and/or type and It changes for the equipment of dehydrating prods plasticated.Elastomeric compound can be dehydrated to required water content, then, The dehydration product of gained is further plasticated, at the same it is dry to required moisture level (for example, about 0.5%~about 10%, such as About 0.5%~about 1%, about 1%~about 3%, about 3%~about 5% or about 5%~about 10%, preferably shorter than 1%, it is all Wt% is all based on the total weight of product).The improvement of rubber performance can be provided by assigning the mechanical energy of material.For example, dehydration product Machine can be carried out with one or more in continuous mixer, mixer, double screw extruder, single screw extrusion machine or roller mill Tool is processed.The optional mixing step, which can have, to be had the capability that：Mixture and/or the generation surface region of plasticating or exposure table Face, this can allow removal to be likely to be present in the water (at least part of it) in mixture.Suitable plasticating equipment is well known And it is commercially available, including, for example, the Unimix from Farrel Corporation of Ansonia, CT, USA Continuous Mixer and MVX (mix, ventilation, squeeze out) machine, coming from Pomini, the elongated continuous mixer of Inc., Pomini Continuous Mixer, birotor rotating Vortex intermeshing extruder, birotor reversely rotate non-intermeshing extruder, Banbury mixer, Brabender mixer, engagement type mixer, kneading formula mixer, continuous compounding extrusion machine, Kobe The twin shaft mixing extruder and Kobe Continuous Mixer of Steel, Ltd. production.Alternative device of plasticating is for this It is known and be that can use for field technology personnel.

When the product through dehydration is handled in required device, which imparts energy to material.It is not only restricted to Any particular theory, it is believed that the product through dehydration is heated in the friction generated during machinery is plasticated.One in the heat It is consumed by heating and vaporizing through the moisture in the product of dehydration a bit.A part of water can also be by concurrently squeezing with heating Material is removed.Temperature should be sufficiently high, with the steaming promptly removed by water evaporation at release to air and/or from device Vapour, but cannot be too high so that rubber is made to burn.Product through dehydration can reach about 130 DEG C~about 180 DEG C of temperature, such as It is about 140 DEG C~about 160 DEG C, especially true when coupling agent is added before or during plasticating.Coupling agent can contain a small amount of Sulphur, and temperature should be maintained at sufficiently low horizontal with rubber cross during preventing from plasticating.

Alternatively, additive can in mechanical mixer with the product composition through dehydration.Specifically, can be to machine Additive is added in tool mixing machine, (it can be identical or different with the filler that is used in mixing machine for example, filler；Illustratively Filler includes silica, carbon black and/or zinc oxide), other elastomers, other or additional masterbatch, antioxidant, coupling agent, increasing Mould agent, processing aid (for example, stearic acid, also is used as curing agent, liquid polymer, oil, wax etc.), resin, fire retardant, increasing Amount oil, and/or lubricant and their any mixture.Additional elastomer can be with the product composition through dehydration to produce Raw elastomer blend.Suitable elastomer be included in any elastomer used in the form of a latex in above-mentioned mixed process and The elastomer not obtained in the form of a latex such as EPDM, and can in the elastomeric compound containing silica elastomer phase with or It is different.Illustrative elastomer includes, but are not limited to：Rubber；1,3- butadiene, styrene, isoprene, isobutene, 2,3- The polymer of dialkyl group -1,3- butadiene (wherein alkyl can be methyl, ethyl, propyl etc.), acrylonitrile, ethylene, propylene etc. (such as homopolymer, copolymer and/or terpolymer).It is special that the method for production blend for masterbatches is disclosed in the jointly owned U.S. In sharp No.7,105,595,6,365,663 and 6,075,084 and PCT Publication WO2014/189826.Antioxidant (degradation suppression The example of preparation) can be amine type antioxidant, phenolic antioxidant, imidazole type antioxidant, carbamate metal salt, P-phenylenediamine and/or dihydro trimethylquinoline, the quinine antioxidant of polymerization, and/or wax and/or in elastomer formulations Other antioxidants.Specific example includes, but are not limited to N- (1,3- dimethylbutyl)-N'- Phenyl-p-phenylenediamines (6-PPD, for example, deriving from the ANTIGENE 6C of Sumitomo Chemical Co., Ltd.s and deriving from Ouchi Shinko The NOCLAC 6C of Chemical Industrial Co., Ltd.), from Seiko Chemical Co., Ltd. " Ozonon " 6C, 1, the 2- dihydros -2,2 polymerizeing, 4- trimethylquinolines (TMQ, such as the Agerite derived from R.T.Vanderbilt Resin D), 2,6 di tert butyl 4 methyl phenol (carries as the Vanox PC from Vanderbilt Chemicals LLC For), butylated hydroxytoluene (BHT) and butylated hydroxy anisole (BHA) etc..Other representative antioxidants can be, for example, Diphenyl-p-phenylenediamine and for example in the 344-346 pages of The Vanderbilt Rubber Handbook (1978) It is disclosed it is other those.

Coupling agent can be or including one or more silane coupling agents, one or more zirconium ester coupling agents, Yi Zhonghuo A variety of titanate coupling agents, one or more nitro coupling agents, or any combination thereof.Coupling agent can be or including bis- (3- tri- Triethoxysilyl propyl) four sulfanes are (for example, Si 69 from Evonik Industries, come from Struktol The Struktol SCA98 of Company), bis- (3- triethoxysilylpropyltetrasulfides) disulphanes (for example, come from Evonik Si 75 and Si 266, the Struktol SCA985 from Struktol Company of Industries), 3- thiocyanos third Base-triethoxysilane (for example, Si 264 from Evonik Industries), γ-mercaptopropyl-trimethoxy silane (for example, the VP Si 163 from Evonik Industries, the Struktol from Struktol Company SCA989), γ-mercaptopropyi-triethoxysilane (for example, VP Si 263 from Evonik Industries), zirconium two New two (3- sulfydryls) propionic acid ester group-O (zirconium dineoalkanolatodi (3-mercapto) of alkanol ester group Propionato-O bis- (2- methyl -2- the nitropropyls) -1,6- diamino hexanes of), N, N'-, S- (3- (triethoxy-silicanes Base) propyl) spicy thioalcohol ester (S- (3- (triethoxysilyl) propyl) octanethioate) is (for example, come from The NXT coupling agents of Momentive, Friendly, WV), and/or be chemically similar or with one or more identical chemical groups Coupling agent.The trade name of other specific examples of coupling agent, includes, but are not limited to the VP from Evonik Industries Si 363.It should be understood that any combinations of elastomer, additive and additional masterbatch can be added to for example in blender The product through dehydration in.

Alternatively, the product through dehydration can be moulded using mixer such as Banbury or Brabender mixer Refining.The product through dehydration can be made to reach about 3wt%~about 40wt% (for example, about 5wt%~about 20wt% or about first 20wt%~about 30wt%) moisture.The moisture can be achieved by the following procedure：It is dehydrated to required level；Alternatively, As first step, the clast of the product through dehydration is dehydrated to medium moisture, then, the warp as obtained by heating is de- The product of water or by make water at room temperature from through dehydration product evaporation or by familiar to the person skilled in the art other Method further decreases moisture.Product through dehydration can be plasticated in mixer, until reaching required moisture water The input of flat or mechanical energy.Product through dehydration can be plasticated until reach scheduled temperature, be allowed to cool, then, primary or more It puts back in mixer secondaryly, to assign material additional energy.The example of temperature includes about 140 DEG C~about 180 DEG C, for example, About 145 DEG C~about 160 DEG C or about 150 DEG C~about 155 DEG C.Through the product of dehydration can be in mixer every time plasticate after Tabletting is carried out in roller mill.Selectively, it or in addition, plasticates in Banbury or Brabender mixer Product through dehydration can further plasticate in open mill.

Alternatively, the product through plasticating can be further processed on a mill.Product through plasticating can be used as extrudate Length be discharged from continuous blender, and can enter open mill before be cut into smaller length.Product through plasticating can appoint Selection of land is transported to open mill by conveyer.Conveyer can be conveyer belt, conduit, pipeline or continuously match for that will come from The product through plasticating of mixed machine is transported to other suitable devices of open mill.Open mill may include a pair of of roller, can be with It is optionally heated or cools down to provide the open mill operability of enhancing.Other operating parameters of open mill may include between roller Clearance distance, piling height (that is, accumulation of the material in gap between roller and on roller top) and each roller speed Degree.The speed of each roller and the temperature of the fluid for cooling down each roller can be controlled separately for each roller.It is described Clearance distance can be about 3mm~about 10mm or about 6mm~about 8mm.Roller speed can be about 15rpm~about 70rpm, and roller can be with Roll toward each other to entrance side relative to grinding machine.Friction is than (collecting drum (for example, collecting the roller of the product through plasticating thereon) Speed and back roller speed ratio) can be about 0.9~about 1.1.For make roller cool down fluid can be about 35 DEG C~about 90 DEG C, for example, about 45 DEG C~about 60 DEG C, about 55 DEG C~about 75 DEG C or about 70 DEG C~about 80 DEG C.Operation in addition to controlling open mill With the level and other than making product through plasticating dry of plasticating needed for providing, also it is desirable to which the output of open mill should be used as smooth Sheet collection on collecting drum.It is not only restricted to any particular theory, it is believed that, colder roller temperature helps to realize the target.It opens The temperature of product through plasticating can be down to substantially about 110 DEG C~about 140 DEG C by mill.Stop of the product through plasticating in grinding machine Time can partly determine by roller speed, clearance distance and the required amount plasticated and dried, also, for having already passed through The material plasticated, for example, in twin rotor continuous mixers, the residence time can be about 10 minutes~about 20 minutes.

It would be recognized by those skilled in the art that the various combination that equipment may be used to manufacture to according to various embodiments The silica containing solid-state continuous rubber phase offer plasticate and dry.Depending on used equipment, different from above-mentioned condition Under the conditions of to be operated to them to assign the different workload of material and drying can be desirably.In addition, using series connection It is more than a kind of certain types of equipment (such as open mill or mixer) or the product through plasticating is made to pass through given equipment More than can be once desirably.For example, the product through plasticating can by open mill twice or thrice or more time, or Person passes through the concatenated open mill of two or three or more.In the latter case, in different operating condition (such as speed The energy input etc. of degree, temperature, difference (such as higher)) under to operate each open mill can be desirably.Product through plasticating Pass through one, two or three open mill after being plasticated in mixer.

The elastomeric compound that can vulcanize can be used for producing elastomer or the product comprising rubber.Alternatively, elastic Nanocrystal composition can be used in following article or be produced in following article：The different piece of tire, for example, wheel Tire, tire tread, sidewall, for the serif covering of tire and for the buffering adhesive of retreads.Selectively, or In addition, elastomeric compound can be used in following article or for producing following article：Hose, sealer, liner, vibrationproof system Product, crawler belt, track pad (the track puopulsion equipment for bull-dozer etc.), engine support, earthquake stability device, winning equipment Such as sieve, winning equipment lining, conveyer belt, chute liner, slurry pump lining, Mud pump components such as impeller, valve seat, valve body, work Plug hub, piston rod, plunger, the impeller for various applications (such as mixed slurry) and slurry impeller of pump, the liner for pulverizing grinding machine, rotation Lining, the hose of wind separator and cyclone hydraulic separators, expansion pipe, marine equipment such as pump (such as slush pump and outboard motor pump) (such as dredging hose and outboard motor hose) and other marine equipments are used for waterborne, oil, aviation and other application Axle envelope, propeller shaft, pipeline for conveying such as oil-sand and/or tar sand lining and wherein need wearability and/ Or the other application of the dynamic property of enhancing.After curing, vulcanized elastomeric compound can be used for wherein needing wearability And/or the roller of dynamic property of enhancing, cam, axis, pipeline, vehicle are in tyre surface bushing or other application.

Traditional compounding technique can be used for sulfiding reagent and other additions known in the art according to required purposes Agent (including previously discussed with the relevant additive of product through dehydration) combines with the elastomeric compound that can vulcanize. After such compounding, material remains able to vulcanize, any sulphur until being added in elastomeric compound or other crosslinking agents The required degree of cross linking is formed in material, for example, when being heated to such as 105 DEG C of suitable temperature, continues required time, example Such as, reach the time of 90% vulcanization (vulcanization is measured by traditional rubber rheometer).Preferably, elastomeric compound is in sulphur Reach the expansion index of about 1.80~about 2.20 (for example, about 1.90~about 2.10 or about 1.95~about 2.05) during change.Ability Field technique personnel are it will be recognized that expansion index can pass through the amount of the selection of accelerating agent, accelerating agent and sulphur, vulcanization time and accelerating agent It is adjusted with the ratio of sulphur.The ratio of accelerating agent and sulphur has an effect on the crosslink type in the presence of rubber.Suitable accelerating agent with And the information about kinetics include it is following in it is those of listed：Vanderbilt Rubber Handbook are (by RT Vanderbilt Company, Inc. publish (the 14th edition, 2010)) and Bayer Manual for the Rubber Industry (Bender etc., Bayer AG, 1993).

The invention further relates to the elastomer that any one or more of method described here is formed through the invention is multiple Close object.

Unless otherwise specified, being all herein in terms of wt% by all material proportions of percents description.

The present invention is will be evident from by following embodiment, these embodiments are substantially merely exemplary.

Embodiment

In these embodiments, " fresh latex " is the fresh latex (Muhibbah that dry rubber content is about 30wt% Lateks Sdn Bhd, Malaysia)." latex concentration object " is dilute using pure water or the water with 0.6wt%~0.7wt% ammonia Release about 50% latex concentration object (the high ammonia grade, from Muhibbah Lateks Sdn for reaching about 30wt% dry rubber contents Bhd, Malaysia, or come from Chemionics Corporation, Tallmadge, Ohio).Unless otherwise stated, " silica " isZ1165MP precipitated silicas, it is (pervious from Solvay USAInc., Cranbury, NJ Rhodia)。

Thermogravimetric analysis.According to 6231 methods of ISO, it is horizontal that practical silica loading capacity is measured by thermogravimetric analysis (TGA).

The water content of product.Test material is cut into the piece of mm in size and be packed into moisture balance (such as MB35 types and MB45 types；Ohaus Corporation, Parsippany NJ) in measure.Water content is measured at 130 DEG C 20 minutes extremely 30 minutes, until test sample reaches constant weight.

Slurry zeta potential.In these embodiments, using from Colloidal Dynamics, LLC, Ponte Vedra The ZetaProbe Analyzer of Beach, Florida USA^TMMeasure the zeta potential of particle slurry.Using multifrequency electroacoustics technology, ZetaProbe directly measures zeta potential under the up to granule density of 60 volume %.The instrument uses Colloidal first The KSiW calibrating fluids (2.5mS/cm) that Dynamics is provided are calibrated.Then, 40g samples are placed in stirring rod In Teflon glasss of 30mL (part number A80031), and this glass is placed in stirring pedestal (part number with the mixing speed of 250rpm A80051 on).It is measured with one-site model using dip probe 173,5 point operations is carried out under environment temperature (about 25 DEG C). The 2.14c Polar of the ZP versions provided by Colloidal Dynamics are provided^TMSoftware analysis data.According to charge on particle Polarity, zeta potential value can be negative value or positive value." magnitude " of zeta potential refers to absolute value (for example, the zeta potential value ratio-of -35mV The zeta potential value of 20mV is high).The electrostatic repulsion degree between similar charged particle in the magnitude reflection dispersion of zeta potential.ζ electricity The magnitude of gesture is higher, and the particle in dispersion is more stable.Zeta potential survey is carried out to the particle shape silica slurry prepared as described below Amount.

It weighs dry silica, also, using 5 gallon bucket and with the high shear overhead type laboratory for shrouding formula blender Mixing machine (Silverson Model AX3, Silverson Machines, Inc., East Longmeadow, MA；In 5200- Operated 30 minutes to 45 minutes under 5400rpm) it is combined with deionized water.Once silica is substantially dispersed in water and can pump It send, then by peristaltic pump, (Masterflex 7592-20 systems-driving and controller, use 73 pipes of I/P to silica slurry 77601-10 is pumped；Cole-Palmer, Vernon Hills, IL) it is transferred to positioned at operation tank (30 gallons of convex bottom opening Container) in online high shear rotor-stator mixer (be located at peristaltic pump after Silverson Model 150LB, Run with 60Hz) mixed circuit in and be ground, to further decomposed silica aggregate and remaining silica granule.So Afterwards, the slurry in the operation tank recycles a period of time, the time using identical peristaltic pump at 2L/min by mixed circuit Be enough volume of the circular flow is made to be at least total slurry volume 5-7 times (>45 minutes) to ensure that it is appropriate that any silica aggregate all passes through Grinding and distribution.Using with the overhead type mixing machine (Ika of the about 60rpm low sheraing anchor formula blades rotated in running tank Eurostar power control visc-P7；IKA-Works, Inc., Wilmington, NC) to prevent silica granule Gelation or sedimentation.After pulverizing, by acid (formic acid or acetic acid, SILVER REAGENT, come from Sigma Aldrich, St.Louis, MO) or Salt (calcium nitrate, calcium chloride, calcium acetate or aluminum sulfate, SILVER REAGENT come from Sigma Aldrich, St.Louis, MO) is added to fortune In slurry in row tank.The amount and acid of silica in slurry or the type of salt and concentration are given in following specific embodiment Go out.

Example process A.It points out in the following embodiments, method is carried out using example process A.In technique A, meter The dry precipitated silica of amount and water (removing the municipal water use of particulate material through filtering) are simultaneously combined, then, in rotor-stator Ground in grinding machine to form silica slurry, also, using blender and another rotor-stator grinding machine, by silica slurry into It is further ground in batch can.Then silica slurry being transferred to dress, there are two in the operation tank of blender.Silica slurry is from operation Tank is recycled by homogenizer and is returned in operation tank.Then by acid, (formic acid or acetic acid, technical grade derive from Kong Long Huat Chemicals, Malaysia) or salt (calcium nitrate, technical grade derive from Mey Chern Chemicals, Malaysia) Solution be pumped into operation tank in.By stirring and optionally, by the circulation loop in running tank, so that slurry holding is in and divide Bulk state.After reasonable time, silica slurry is sent by homogenizer by closed reaction zone (13) as shown in Figure 1a. The concentration of silica concentration and acid or calcium nitrate in slurry provides in following specific embodiment.

Latex is pumped into reaction zone (13) with peristaltic pump (under less than about 40 gauge pressures) by second entrance (11).Latex flows Rate adaptation is loaded between about 300-1600kg latex/hr to obtain required productivity and silica in products obtained therefrom Amount is horizontal.The slurry of the combination containing acid or salt or acid and salt of homogenizing is pumped into nozzle (internal diameter from voltage balancer under stress (ID) it is 0.060 " -0.130 ") (3a) (shown in the first entrance (3) in Fig. 1 (a)), so that slurry is introduced as high-speed jet Reaction zone.When being contacted with the latex in reaction zone, with the silica slurry jet stream that the speed of 25m/s~120m/s flows carry secretly with The latex of 1m/s~11m/s flowings.In the embodiment according to embodiments of the present invention for successfully generating elastomeric compound, Silica slurry causes silica granule to be mixed with the close of the rubber grain of latex the impact of latex, also, rubber agglomerates, Convert silica slurry and latex to such material, it includes 40~95wt% water (bases containing capture in the material In the total weight of the material) the silica containing solid-state or semisolid continuous rubber phase.To silica slurry flow rate (500- 1800kg/hr) or latex flow rate (300-1800kg/hr) or the two are adjusted, to change in the final product The ratio (such as silica of 15-180phr) of silica and rubber, and reach required productivity.Productivity (be based on dry matter) is 200-800kg/hr.The specific silica content in the rubber after material dehydration and drying is listed in the following embodiments (being analyzed by TGA).

Method A dehydrations.Material is discharged into the flow rate of 200 to 800kg/hr (dry weights) from reaction zone de- under atmospheric pressure In water extruder (French Oil Machinery Company, Piqua, OH).The extruder (8.5 inch inner diameter) equipped with The template that button constructs (die-hole buttons configuration) is connect with various die holes, and with 90~123RPM's The Power operation of typical rotor speed, the die plate pressure of 400-1300psig and 80kW~125kW.In the extruder, it will contain The rubber of silica compresses, also, the water squeezed out from the rubber containing silica is discharged by the fluting machine barrel of extruder.In extruder Exit obtain the typically product through dehydration containing 15-60wt% water.Then, the product through dehydration is sent to method A Drying and cooling technique, alternatively, being further dehydrated with the dewatering process of method B, and be then sent to and hereafter further retouch The drying of the method B stated and cooling technique, as shown in table 5.

Method A is dry and cooling.As noted, the product through dehydration is put into continuous blender (Farrel Continuous Mixer (FCM), Farrel Corporation, Ansonia, CT；7 and No. 15 rotors) in, continuously match at this In mixed machine, be dried, plasticate and with 1-2phr antioxidants (such as from Flexsys, the 6PPD of St.Louis, MO) and times Choosing silane coupling agent (such as NXT silane derives from Momentive Performance Materials, Inc., Waterford, NY；8wt% silane, in terms of silica weight) mixing.The temperature of FCM water legs is set as 100 DEG C, exports aperture The FCM temperature at place isThe moisture for leaving the dehydration elastomeric compound through plasticating of FCM is about 1wt%~5wt%.Product is further plasticated and cooled down on a mill.By the sheet rubber of elastomeric compound directly from opening It cuts in mill, roll and cools down in air.

Example process B.It points out in the following embodiments, illustrative methods is carried out using example process B.In method In B, dry silica of weighing, also, mixed using 5 gallon bucket and with the high shear overhead type laboratory for shrouding formula blender Machine (Silverson Model AX3, Silverson Machines, Inc., East Longmeadow, MA；In 5200- Operated 30 minutes to 45 minutes under 5400rpm) it is combined with deionized water.Once silica is substantially dispersed in water and can pump It send, then by peristaltic pump, (Masterflex 7592-20 systems-driving and controller, use 73 pipes of I/P to silica slurry 77601-10 is pumped；Cole-Palmer, Vernon Hills, IL) it is transferred to positioned at operation tank (30 gallons of convex bottom opening Container) in online high shear rotor-stator mixer (be located at peristaltic pump after Silverson Model 150LB, Run with 60Hz) mixed circuit in and be ground, to further decomposed silica aggregate and remaining silica granule.So Afterwards, the slurry in the operation tank recycles a period of time at 2L/min by mixed circuit, which is enough to make volume of the circular flow at least For total slurry volume 5-7 times (>45 minutes) to ensure that any silica aggregate all passes through grinding appropriate and dispersion.It is running Using with overhead type mixing machine (the Ika Eurostar power of the about 60rpm low sheraing anchor formula blades rotated in tank control visc-P7；IKA-Works, Inc., Wilmington, NC) to prevent the gelation or sedimentation of silica granule. After pulverizing, by acid (formic acid or acetic acid, SILVER REAGENT come from Sigma Aldrich, St.Louis, MO) or salt (calcium nitrate, chlorination Calcium, calcium acetate or aluminum sulfate salt, SILVER REAGENT come from Sigma Aldrich, St.Louis, MO) it is added to the slurry in operation tank In.It has been given in Table 5 the type and concentration of the silica amount in the slurry and acid or salt for following specific embodiment.

Using peristaltic pump, (Masterflex 7592-20 systems-driving and controller, use the 77601-10 of 73 pipes of I/P Pump；Cole-Palmer, Vernon Hills, IL), make latex pumping by second entrance (11) and enters similar to Fig. 1 (b) The reaction zone (13) of shown configuration.Latex flow rate is adjusted between about 25kg/h~about 250kg/h multiple to change elastomer Close the ratio of the silica and rubber of object.

When silica is well dispersed in water, by diaphragm metering pump (LEWA-Nikkiso America, Inc., Holliston, MA) slurry is pumped through pulsed damper from operation tank (to reduce the pressure caused by diaphragm action Fluctuation), enter in reaction zone or operation tank via circulation loop " T " connector.The direction of slurry is controlled by two pneumatic ball valves, One guides slurry to reaction zone, and another guides slurry to operation tank.When preparation mixes silica slurry with latex When, by close two valves, by supply lead to reaction zone first entrance (3) pipeline be forced into 100psig~ 150psig.Then, it opens and guides slurry to the ball valve of reaction zone, also, at initial pressure 100psig to 150psig, Pressurization silica slurry is fed in nozzle shown in Fig. 1 (b) (ID0.020 '~0.070 ") (3a), makes slurry as high-speed jet Introduce reaction zone.When being contacted with the latex in reaction zone, with the jet stream for the silica slurry that the speed of 15m/s~80m/s flows Carry the latex flowed with 0.4m/s~5m/s secretly.In the reality according to embodiments of the present invention for successfully generating elastomeric compound It applies in example, silica slurry causes silica granule to be mixed with the close of the rubber grain of latex the impact of latex, also, rubber is sent out Raw cohesion, converts silica slurry and latex to such elastomeric compound, and it includes silica granules and capture containing solid The water of state or 40wt%~95wt% in the continuous rubber phase of semisolid silica.To silica slurry flow rate (40kg/hr~ 80kg/hr) or latex flow rate (25kg latex/hr~300kg latex/hr) or the two are adjusted, to change in institute The ratio (such as silica of 15-180phr) of silica and rubber in the product obtained, and reach required continuous production rate (30kg/hr~200kg/hr is based on dry matter).Listed in the following examples dehydration and it is dry after specific silica and Ratio (phr) content of rubber.

Method B dehydrations.

The material being discharged from reaction zone is collected and is clipped between two blocks of aluminium sheets in trapping disk.It then should " Sanming City Control " it is inserted between two pressing plates of hydraulic press.When applying 2500 gauge pressure on aluminium sheet, the water captured in rubber product is squeezed Go out.If desired, by the folding of material through extruding at smaller block, and the extrusion process is repeated using hydraulic press, until rubber The water content of product is less than 40wt%.

Method B is dry and cooling.Product through dehydration is put into Brabender mixer (300cc) be dried and It plasticates, forms the dehydration elastomeric compound through plasticating.Enough materials through dehydration are fitted into mixing machine to cover rotor. The initial temperature of mixing machine is set as 100 DEG C, and spinner velocity is generally 60rpm.Remain in the water in the product through dehydration mixed It is converted into steam during closing and is evaporated from mixing machine.It is necessary when the material in mixing machine is expanded due to evaporation When remove the material of any spilling.Silane coupling agent (NXT silane is obtained from Momentive Performance Materials, Inc., Waterford, NY；8wt% silane is based on silica weight) and/or antioxidant (6-PPD, N- (1,3- dimethyl butyrate Base)-N'- Phenyl-p-phenylenediamines, Flexsys, St.Louis, MO) it is optionally added into when mixing machine temperature is higher than 140 DEG C Into mixing machine.When the temperature of mixing machine reaches 160 DEG C, the material inside mixing machine before material is toppled over by changing rotor Speed 2 minutes and be maintained at 160 DEG C~170 DEG C.Then, the dehydration elastomeric compound through plasticating is processed on a mill. The moisture of the material taken out from grinding machine is usually less than 2wt%.

The preparation of Rubber compound.

The drying elastomeric compound obtained by any method outlined above according in Table A formula and table B in it is general The process stated is compounded.For the silica elastomeric compound of silane or antioxidant is added in the drying process, final Blend is formed as defined in Table A.Adjust accordingly the silane coupling agent and/or antioxidant added during compounding Amount.

Table A

* N- (1,3- dimethylbutyl)-N'- Phenyl-p-phenylenediamines (Flexsys, St.Louis, MO)

* main active components：S- (3- (triethoxysilyl) propyl) spicy thioalcohol ester (S- (3- (triethoxysilyl) propyl) octanethioate) (Momentive, Friendly, WV)

* * diphenylguanidine (Akrochem, Akron, OH)

* * * N- tertiary butyl benzothiazole -2- sulfenamides (Emerald Performance Materials, Cuyahoga Falls, OH)

NR=natural rubbers

S=is as described

Table B

Implement vulcanization in the hot press for being set as 150 DEG C, determines vulcanization time (that is, T90 by traditional rubber rheometer The 10% of+T90, wherein T90 are the time for realizing 90% vulcanization).

The property of rubber/silica mixing material.

The elongation at break of the continuous rubber phase of the silica containing solid-state is straight by stretching the material collected from reaction zone manually It is broken to it and is measured with reference to measured length dimension.The draftability of cured samples is measured according to ASTM standard D-412 Energy (T300 and T100, elongation at break, tensile strength).Under 0.01%~60% torsion, at 10Hz and 60 DEG C, use Dynamic strain scanner measures 60 ° of tan δ.Tanδ_{It is maximum}(being listed in the following table as tan δ 60) is considered to be at the range of strain The maximum value of interior tan δ 60.

Comparative example 1.

Using 20 natural rubbers of SMR (Hokson Rubber) and Z1165 silicas, (wherein used using the formula in Table A NXT silane) and table 1 in compounding scheme prepare dry-mixed silica organic elastomer compound.Sample is vulcanized as described above. The engineering properties of gained sulfur product is listed in table 2.

Table 1

Table 2

Embodiment 2.

There is 27.8wt% as discussed previously with respect to preparing as described in slurry zeta potential test method1165 silicas Silica slurry.Then, the supernatant diluted slurry obtained with deionized water or from the ultracentrifugation of 27.8wt% slurries, with system A series of standby silica slurries with various silica concentrations.The zeta potential for measuring various silica slurries, to show the silica in slurry Relationship between concentration and the zeta potential of slurry.As shown in table 3A, the zeta potential of silica slurry seems to depend on using deionized water Prepare silica concentration when silica slurry.However, as shown in table 3B, obtained from the ultracentrifugation of 27.8wt% slurries when use When supernatant diluted slurry, the zeta potential under different silica concentrations keeps roughly the same.

Table 3A uses the zeta potential of silica slurry made of deionized water.

Silica concentration (w/w) in slurry	6%	10%	15%	20%	22%	25%
							Zeta potential (mV)	-46.4	-42.7	-39.6	-36.2	-34.7	-32.3
pH	5.19	5.04	4.92	4.86	4.83	4.77

Table 3B with the supernatant of 27.8wt% silica slurries diluting silica slurry made of 27.8wt% silica slurries Zeta potential.

Silica concentration (w/w) in slurry	6%	22%
			Zeta potential (mV)	-31.5	-31.4
pH	4.86	4.79

Should the result shows that, when such silica slurry is diluted with deionized water, the increase of the magnitude of zeta potential mainly by In the reduction of the ionic strength of slurry.It is believed that the ion in silica slurry comes from remaining salt, the salt is present in from silicon In the silica of stone particle manufacturing process.The high magnitude of the zeta potential of silica slurry shows (all more than 30mV)：Silica is in slurry In have high electrostatic stability.

Embodiment 3.

Table 4 lists the influence of salt or acid that various concentration is added into silica slurry to the zeta potential of these slurries.Pass through Above-mentioned slurry zeta potential test method prepares slurry in deionized water.Data in table 4 illustrate silica slurry and through going to stablize Dependence of the zeta potential of the silica slurry of change to silica concentration, salinity and acid concentration.Salt is added in silica slurry or acid can The amount for reducing zeta potential, to reduce the stability of silica slurry.Salt or acid are added in silica slurry reduces the amount of zeta potential Value, to reduce the stability of silica slurry.As shown in table 4, zeta potential depends primarily in the slurry of slurry or stabilization removal Salt or acid concentration, and be not dependent on silica concentration.

The unstability of the zeta potential and silica of slurry of the table 4 under different slurry concentrations, salinity and acid concentration.

ND=is not measured.

Result shown in table 4 illustrates the zeta potential of silica slurry and the silica slurry through stabilization removal to acetic acid concentration and silicon The dependence of stone concentration.Statistics indicate that zeta potential value relys more on acid concentration than silica concentration.For formic acid, zeta potential is observed Similarity relation between acid concentration and silica concentration.Under given concentration, formic acid reduces more zeta potential amounts than acetic acid Value.As shown in table 4, the combination of formic acid and calcium chloride is effective to reducing zeta potential magnitude.Table 4 the result shows that, pass through addition The combination of destabilizing agent such as acid or salt or acid and salt, can efficiently reduce the stability of the silica granule in slurry.For nitre Sour calcium and calcium acetate observe similar result.

Embodiment 4.

In this embodiment, it was confirmed that make the dispersion of silica granule before silica dispersion is contacted with elastomer latices Unstable importance.Specifically, carrying out four experiments, the mixing arrangement (c) equipment using the mixing arrangement (c) in Fig. 1 There are three entrances (3,11,14) to be used to up to three fluids introducing closed reaction zone (13) so that a fluid is with 90 Spend angle as high-speed jet with other fluids of the speed impacts of 15m/s~80m/s (referring to Fig. 1 (c)).Three tested at this four In a, silica is ground as described in method B, and optionally, acetic acid is added as described in following example 4-A to 4-D. Then the slurry of slurry or stabilization removal is forced into 100psig to 150psig, and by entrance (3) with 60 ls/h of (L/ Hr rate of volume flow) is fed to closed reaction zone so that the slurry of slurry or stabilization removal is using 80m/s as high rapid fire Stream introduces reaction zone.Meanwhile by peristaltic pump with the speed of the rate of volume flow of 106L/hr and 1.8m/s, to second entrance (11) natural rubber latex concentrate is introduced in, and (60CX12021 latex, the dry rubber content of 31wt% come from Chemionics Corporation, Tallmadge, Ohio are diluted with deionized water).It selects these rates and adjusts flow to be included The elastomer composite Tetramune of the silica of 50phr (part/100 weight dry rubber substance).The silica slurry of silica slurry or stabilization removal It is by mixing as follows with latex：The low speed latex stream and high-speed jet for making the slurry of silica slurry or stabilization removal pass through entrainment Latex stream in the jet stream of silica slurry or the silica slurry of stabilization removal combines at shock point.Productivity (in terms of dry matter) It is set as 50kg/hr.The following examples list specific practical silica in the rubber composite produced by this method and Rubber ratio.TGA is carried out after the drying according to the method for method B.

Embodiment 4-A：

First fluid：Going for the 25wt% silicas containing 6.2wt% (or 1.18M) acetic acid is prepared as described in above method B Stabilized water-borne dispersions.The zeta potential of the slurry of stabilization removal is -14mV, is shown：Acid is so that slurry is obviously unstable.It will The silica slurry of stabilization removal is continuously pumped into first entrance (3) under stress.

Second fluid：Elastomer latices are supplied by second entrance (11) to reaction zone.

In the reaction region, first fluid collides with second fluid.

As a result：When low speed latex stream by being brought into the silica slurry of stabilization removal by the silica slurry and latex of stabilization removal High-speed jet in and when closely mixing, liquid occurs in the reaction region to consolidating phase reversal.In entrainment process, silica is close Ground is distributed in latex, and mixture coagulated is at the solid phase of the water containing 70wt%~85wt%.As a result, the outlet in reaction zone (15) Place obtains the stream of the continuous rubber phase in the silica containing solid-state of worm or rope form shape.The compound has elasticity and can be The 130% of original length is stretched in the case of not rupturing.The TGA of desciccate is analysis shows elastomeric compound contains The silica of 58phr.

Embodiment 4-B：

First fluid：The aqueous of the stabilization removal of the 25wt% silicas containing 6.2wt% acetic acid is prepared according to above method B Dispersion.The zeta potential of slurry is -14mV, is shown：Acid is so that slurry is obviously unstable.The silica slurry of stabilization removal is being pressed First entrance (3) is continuously pumped under power.

Third fluid：Deionized water is also by third entrance (14) with the speed of the rate of volume flow of 60L/hr and 1.0m/s Degree injection reaction zone.

In the reaction region, these three fluids meet and impinging one another.

As a result：Liquid occurs in the reaction region to solid phase reversal, also, is obtained from the outlet of reaction zone in worm or rope The continuous rubber phase of the silica containing solid-state or semisolid of shape shape.A large amount of turbid liquids containing silica and/or latex with containing solid State or the continuous rubber phase of semisolid silica are flowed out from outlet (7).Continuous rubber phase containing silica contains about 70wt%~about The water of 75wt%, the weight based on compound.The TGA of desciccate is analysis shows that elastomeric compound contains the silica of 44phr. Therefore, water is added by third entrance and negative effect is produced to technique, generate silica content lower product (44phr, phase Than the 58phr in embodiment 4-A) and significant waste product.

Embodiment 4-C：

First fluid：Prepare the 10wt% acetic acid aqueous solutions without silica.Using peristaltic pump with the volume flow of 60L/hr The continuous feed of sour fluid is pumped into reaction zone by dynamic rate by third entrance (14), and when entering reaction zone, speed is 1.0m/s。

Second fluid：Elastomer latices are by second entrance (11) by peristaltic pump with the speed of 1.8m/s and 106L/hr Rate of volume flow is supplied to reaction zone.

In the reaction region, both fluids meet and impinging one another.

As a result：Form solid vermiform bala gutta phase.The TGA of desciccate is analysis shows that solid rubber is mutually free of Silica.

Embodiment 4-D：

First fluid：The silica water-borne dispersions of the 25wt% without acetic acid are prepared according to above-mentioned method B.Silica is starched Material under stress at the point for entering reaction zone the speed of 80m/s and the rate of volume flow of 60L/hr be continuously pumped into first In entrance (3).The zeta potential of slurry is -32mV, is shown：Silica is dispersed stably in slurry.Therefore, in the present embodiment 4-D In, before impacting latex fluids by acid is added into slurry stabilization removal does not occur for silica slurry.

Second fluid：Elastomer latices are passed through by peristaltic pump with the rate of volume flow of the speed of 1.8m/s and 106L/hr Second entrance (11) is supplied to reaction zone.

Third fluid：It, will by third entrance (14) after the starting stage of the continuous flow of the first and second fluids 10wt% acetic acid aqueous solution is to increase to the rate of volume flow of 60L/hr from 0L/hr and increase to the speed of 1.0m/s from 0m/s Degree is injected into reaction zone.In the reaction region, all three fluids are impinging one another and mix.

As a result：Initially, before injection acid, the continuous rubber phase containing silica is not formed, moreover, only turbid liquid is from anti- Answer area outlet (15) discharge.When acid injects reaction zone (13), as acetic acid is increased to by the flow of third entrance from 0L/hr 60L/hr initially forms the continuous rubber phase of the vermiform silica containing semisolid.Still contain from the material of outlet outflow notable The turbid liquid of amount shows the waste for having significant quantity.The TGA of desciccate analysis shows that：It is formed in experiment operation Continuous rubber phase containing the silica only silica containing 25phr.Based on selected working condition and silica usage amount, if silica It has been substantially integrated into the rubber phase containing silica (as described in embodiment 4-A), then generation is comprised more than 50phr silicon by silica The rubber phase containing silica of stone.

These experiments show to obtain the required continuous rubber phase containing silica, and silica slurry is with elastomer latices It must stabilization removal before first Secondary Shocks.Embodiment 4-A, which is realized, is considered in the continuous rubber phase of the silica containing solid-state effective The example of silica is captured, and embodiment 4-D illustrates the comparison technique using the silica slurry of original stable and shows profit With the efficiency of the embodiment 4-A of the silica slurry of initial stabilization removal less than half.It observes and leaves reaction zone exit point Turbid liquid shows：The undercompounding of silica and latex, and capture in continuous rubber phase the silica of less ratio.According to pushing away It surveys, in comparing technique 4B and 4D, the stabilization removal of the fluid in mixed process is insufficient.As a result it further demonstrates that, when It adds additional fluid and undesirable silica capture occurs when simultaneously mixing first fluid and second fluid, also, Such process conditions generate undesirable amount of waste.

Embodiment 5.

In these embodiments, the method for producing elastomeric compound according to various embodiments of the present invention exists It is as shown in table 5 it is various under the conditions of run in the device shown in Fig. 1 ((a) or (b)), using above method A or method B. Selection operation condition is to generate the continuous rubber of the silica containing solid-state or semisolid of the ratio with silica and rubber described in table 5 Glue phase.

Table 5

N/A=is not applicable

A. embodiment 32,33 and 40 (with the precipitated silica that silane coupling agent is handled, is derived from using 454 silicas of Agilon PPG Industries Inc.).Embodiment 50 and 51 uses(conventional precipitated silica, derives from 175GR silicas Solvay S.A.).All other embodiments useZ1165MP precipitated silicas.

B. embodiment 34,39,44 and 52 uses fresh latex.All other embodiments use latex concentration object.

C. the flow rate of slurry and latex is silica slurry and latex fluids respectively when they are transported to reaction zone The rate of volume flow in terms of L/ hours.

D. inlet nozzle speed is that silica slurry is reached before contacting latex by the nozzle (3a) at first entrance (3) Speed when reaction zone (13).

E. zeta potential value by the determining zeta potential of experiment and the salt of the slurry of same levels silica or the concentration of acid according to It deposits relation curve and carries out interpolation method to be estimated.

F.A and B indicates the drying and dehydration of foregoing method A and B." C " expression is dehydrated according to method A, with The additional dehydration and drying according to method B is carried out afterwards.The dehydration of any repetition all indicates the dewatering of repetition methods A.

In all embodiments, selected operating condition all produces the continuous rubber of the substantial cylindrical silica containing solid-state Phase.The product contains the water of more amount, has elasticity and compressibility, and water is discharged in manual compression and keeps in solid It is tolerant.Observe that silica granule is uniformly distributed in entire continuous rubber phase, and the product on outer surface and inner surface all It there is no free silica granule and larger silica particle.In order to form the continuous rubber phase of the silica containing solid-state, not only It needs to make silica stabilization removal (for example, by using acid and/or salt treatment in advance) and it is necessary to adjust the silica slurry of stabilization removal The rate of volume flow relative to latex is expected, not only to obtaining the ratio of required silica and rubber in elastomeric compound (phr), and the mixing rate and latex rubber particle of the degree for equlibrated slurry stabilization removal and slurry and latex it is solidifying Poly- rate.Adjustment in this way makes silica granule be tightly distributed in rubber, latex since silica slurry carries latex secretly In rubber become solid continuous phase, all these is all a few minutes after combining fluid in the limited bulk of reaction zone One of complete in the second.Therefore, this method passes through with the continuous of enough speed, selected fluid-solid object concentration and volume Fluid impact step forms unique silica elastomeric compound, and adjusts the flow rate of fluid so that tiny particle shape Silica uniformly and is tightly distributed in latex, and parallelly, with the generation of such distribution, cause the liquid of rubber to Gu phase reversal.

Comparative example 6.

In these comparative examples, identical basic step and device with described in embodiment 5, still, needle in table 6 have been used Fail to be formed the continuous rubber phase of solid-state or semisolid to the combination of the selected process conditions of each comparative example, and silicon can not be generated Stoneshot elastomer composite.The following table 6 list silica concentration in slurry and the concentration (if any) of acetic acid or calcium nitrate with And the other details of these embodiments.

Table 6

6 (Continued) of table

N/A=is not applicable.

A. zeta potential value by the determining zeta potential of experiment and the salt of the slurry of same levels silica or the concentration of acid according to It deposits relation curve and carries out interpolation method to be estimated.

B. inlet nozzle speed is that silica slurry is reached before contacting latex by the nozzle (3a) at first entrance (3) Speed when reaction zone.

D. embodiment 6-11 and 6-12 is used454 silicas.

Comparative example 6-8,6-9 and 6-10 are shown, even if being used to produce elastomer using according to embodiments of the present invention When the remaining processing step of the preferred method of compound, in the slurry not in the case of the advance stabilization removal of silica, also not Generate the continuous rubber phase containing silica.Comparative example 6-1,6-2,6-3,6-4,6-5,6-6 and 6-7 show to make starching even if in advance Silica stabilization removal (zeta potential of silica is less than 25mV) in material, can not be in reaction zone relative volume when fluid mixes Flow rate and destabilizing agent (such as Ca (NO₃)₂Or acetic acid) the combination of dilution manufacture the continuous rubber phase containing silica. It is not only restricted to any theory, it is assumed that the slurry in reaction zone and the destabilizing agent in the mixture of latex is such low dense Degree can reduce the cohesion rate of latex rubber particle so that continuous rubber cannot be formed in short residence time in the reaction region Phase.In comparative example 6-1, using the silica slurry of the stabilization removal of 18.5wt% and the DRC latex concentration objects of 30.6wt%, go The relative flow ratio of stabilized slurry and latex is set as 0.73 (V/V), to provide silica/rubber of 50phr to reaction zone Glue ratio.It is assumed that under volume flow ratio relatively low as stabilization removal slurry and latex, latex rubber particle exists It is not agglomerated in 0.48 second residence time of the mixture in reaction zone, as a result, in the reaction region, the silica slurry of stabilization removal In 14.8mM Ca (NO₃)₂Original concentration is diluted 58% and reaches 6.2mM.Therefore, it can not possibly produce and contain under these conditions The continuous rubber phase of the silica containing solid-state or semisolid of 50phr silicas.Use higher salinity (for example, invention is real however, working as Apply 0.22wt%s of the 0.5wt% of a 5-37 relative to comparative example 6-1) (the zeta potentials of -17.1mV relative to -22mV) and slurry When being set as 2.1 rubber to generate the silica containing 50phr with the volume flow ratio of latex, suitable product is produced.Comparison Example 6-3 shows setting for 0.57 volume flow ratio (V/V) of slurry and fresh latex in 40phr silicas and stabilization removal The continuous rubber phase of the silica containing solid-state can not be produced by setting down.Higher slurry/latex volume flow ratio will cause reacting The dilution of salt in area is less than comparative example 6-3, therefore generates the continuous rubber phase of the silica containing solid-state.

Salinity in the silica slurry of 18.5% stabilization removal of comparative example 6-2 is 0.48%, and zeta potential is -17mV, Show：The degree of stabilization removal is equally matched with inventive embodiments 5-41 (- 14.1mV), still, selected in comparative example 6-2 The lower company without forming the silica containing solid-state of production setting of the latex concentration object of 30phr silica contents and relatively low flow rate Continuous rubber phase.It is not intended to be limited to any theory, it is believed that in comparative example 6-2, the silica slurry of salt and/or stabilization removal passes through The cohesion rate of the rubber latex particles in reaction zone is too greatly reduced by the excessive dilution of the latex concentration object of reaction zone, So that coherent continuous rubber phase can not be formed in 0.36 second residence time in reaction zone.

When by fresh latex and 10wt% via 0.65%Ca (NO₃)₂Stabilization removal silica slurry (zeta potential be- When 15.4mV) mixing, comparative example 6-5 is 60phr in the ratio of silica and rubber and slurry/latex volume flow ratio is 0.57 When do not generate the continuous rubber phase of the silica containing solid-state.These conditions do not transport the slurry of enough salt and/or stabilization removal To reaction zone to make rubber latex particles quickly agglomerate in reaction zone.In general, it is sufficient to agglomerate the silica of latex concentrate Stabilization removal degree and/or slurry/Latex flow ratio of slurry are insufficient to allow fresh latex to agglomerate.

When using silica slurry stabilization removal of the acid to make comparative example 6-6 and 6-7, similar result is obtained.Work as use When acid is as the sole agent for making silica slurry stabilization removal, slurry in reaction zone and there are acid/ammonia in the mixture of latex The preferred threshold value of molar ratio is less than the value, then the continuous rubber phase of the silica containing solid-state or semisolid will not be formed in the reaction region. In these experiments, required acid/ammonia molar ratio threshold value is always above 1.0, as a result, leaving the pH value of the product of reaction zone is Acid.In the case of comparative example 6-6 and 6-7, the silica/rubber ratio production for being respectively 20phr and 25phr is set It sets, uses 0.28 and 0.36 low slurry/latex volume flow ratio respectively.Under these low flow-rate ratios, Acid Slurry Acidity be not enough to neutralize latex in ammonia.The acid of comparative example 6-6 and 6-7/ammonia molar ratio are respectively 0.66 and 0.98.At this In the case of two kinds, only muddy liquid sprays reaction zone.Slurry will be come from using higher slurry/latex volume flow ratio Enough acid be sent into reaction zone to neutralize the ammonia from latex.

Embodiment 7.

In order to explore the state-variable for the continuous rubber phase that can form the silica containing solid-state or semisolid, in state-variable A series of experiments is carried out under various combinations, the silica that the state-variable includes, but are not limited in the slurry of stabilization removal is dense Degree, stabilization removal slurry in acid or the concentration of salt, the type of latex (such as fresh latex and latex concentration object), latex in Ammonia density, latex batch, the flow rate of the slurry of stabilization removal and latex, stabilization removal in reaction zone slurry and glue The speed of breast and the concentration of acid or salt in reaction zone.The experiment of the series is carried out according to method A, and is made using calcium nitrate For salt.It is directed to latex concentration object and fresh latex respectively, the solid content of fluid and the entrance of experiment are listed in table 7A and 7B Nozzle velocity.Under the volume flow ratio (that is, low silica/rubber ratio in reaction zone) of low slurry and latex, go Stabilized slurry and salt are diluted by latex, and do not form the continuous rubber phase of the silica containing solid-state or semisolid.Then, by carrying The setting of silica/rubber ratio is gradually increased in high slurry/latex volume flow ratio, until observing silicon containing solid-state or semisolid The continuous rubber phase of stone leaves reaction zone.In table 7A and 7B, " the silica loading capacity for being transmitted to reaction zone " indicates to generate containing solid Minimum silica/rubber ratio when state or the continuous rubber phase of semisolid silica.It calculates and is directed to every group of experiment condition (example Such as, the silica concentration in slurry, the salinity in slurry, slurry velocity) (including the slurry of stabilization removal and latex) it is anti- Answer the minimum salinity of the continuous rubber phase for being used to form the silica containing solid-state or semisolid in area.Before being listed in table 7A 6 embodiments, the silica concentration in the slurry of stabilization removal is identical (i.e. 18.5wt%), still, in the slurry of stabilization removal Salinity is different, moreover, in each example, use is determined by increasing latex rate of volume flow up to forming condensation product In the lower threshold value of the silica loading capacity for the continuous rubber phase for forming the silica containing solid-state or semisolid.Result table in table 7A It is bright, when the salinity in the silica slurry of stabilization removal is increased to 0.75wt% from 0.22wt%, slurry/latex can be reduced Volume flow ratio, to obtain the continuous rubber phase of the silica containing solid-state or semisolid with lower silica/rubber ratio.Example Such as, it by making salinity be increased to from 0.22wt% the 0.65wt% of 18.5wt% silica slurries, is used to form containing solid-state or half The minimum silica phr setting values of the continuous rubber phase of solid-state silica are reduced to 35phr silicas from 80phr silicas, because latex Relative volumetric flow increases and the ratio of slurry/latex rate of volume flow is reduced to 0.51 from 1.17.Other silicas are starched Material concentration and when also observing similar result when making silica slurry stabilization removal using acid.

The formation threshold value of the continuous rubber phase of table 7A. silicas containing solid-state or semisolid：Silica loading capacity phr and calcium nitrate are dense Degree, under various conditions, when stabilization removal silica slurry with 50% diluted latex concentrate (31wt% dry rubber contents； 0.70wt% ammonia contents, other than last sample (its ammonia content is 0.53wt%)) mixing when, application method A.

Table 7A

A. inlet nozzle speed is that silica slurry is reached instead before contacting latex by the nozzle (3a) of first access point Answer speed when area.

The formation threshold value of the continuous rubber phase of table 7B. silicas containing solid-state or semisolid：Silica loading capacity phr and calcium nitrate are dense Degree, under various conditions, when silica slurry is mixed with fresh latex, application method A.

Table 7B

A. inlet nozzle speed is that silica slurry is reached before contacting latex by the nozzle (3a) at first entrance (3) Speed when reaction zone.

In the batch-type carried out by mixing silica slurry in bucket with latex under relatively low shear-mixed Cohesion experiment in, for the latex in cohesion mixture salt or acid minimum be it is constant, with mix before silica slurry In salt or acid original concentration it is unrelated.However, in various embodiments according to the present invention for producing elastomer composite In the preferred method of object, it is used to form the threshold concentration of the salt in the reaction zone of the continuous rubber phase of the silica containing solid-state or semisolid With the increase of the salinity (i.e. the stabilization removal degree of silica slurry) in the silica slurry of stabilization removal before mixing Increase.For example, in table 7A, it can be seen that the Ca (NO for agglomerating latex concentrate₃)₂The slurry of threshold concentration and stabilization removal Silica concentration in material is unrelated, but depends strongly on the original salinity in the silica slurry of stabilization removal.When salt is dense When degree increases to 69.3mM from 14.8mM, threshold value salinity increases to 23.0mM from 7.9mM.In order to be compared, cut using low It cuts stirring and carries out a series of intermittent cohesion experiments in bucket, and determine, for condensed phase with the Ca (NO of latex concentration object₃)₂ Threshold concentration is constant at 10.7mM, with the original salinity and stabilization removal in the silica slurry of stabilization removal Silica concentration in slurry is unrelated.These results highlight the stabilization removal degree for balancing silica slurry, mixing rate, silica The aggregation rate of grain and emulsion condensation rate under high shear are for effectively producing the continuous of the silica containing solid-state or semisolid The importance of rubber phase.

Similarly, the continuous rubber phase according to embodiments of the present invention for being used to form the silica containing solid-state or semisolid The threshold value of acid/ammonia ratio is not constant, increases with the sour stabilization removal degree of silica slurry.

Based on manufacturing variables as described herein (for example, the speed of the silica slurry of stabilization removal, the speed of latex, go it is steady Surely the slurry of the relative flow rates of the silica slurry and latex fluids changed, the stabilization removal degree of silica slurry, stabilization removal In silica concentration, latex dry rubber content and latex ammonia density (for example, ammonia density can by by nitrogen bubbling pass through Latex carries out nitrogen bubbling on the top of liquid surface and reduces)), it can obtain and/or predict in required silicon The formation of the continuous rubber phase of the silica containing solid-state or semisolid within the scope of stone loading capacity.Therefore, this of the invention is used to produce The method of elastomeric compound can be operated in the range of variables of optimization.

Comparative example 8.

As the comparison of the continuous process for being successfully produced elastomeric compound with embodiment according to the present invention, into The following comparative experiments gone using multi-step batch process.

In these comparative examples, under the conditions of batch-mixed, using ground silica slurry (in such as above method B Method) or the not ground and silica slurry for preparing (the respective concentration of two kinds of slurries is respectively：25wt% and 6wt% (are based on The total weight of slurry)), so that silica slurry is combined with elastomer latices.The silica used in these embodiments was1165MP.The elastomer latices used in all experiments are the high ammonia that 50% (weight) is diluted with deionized water Latex concentration object (60CX12021, come from Chemionics Corporation, Tallmadge, Ohio).

Test 8-A：Use the batch-mixed of ground silica slurry.

Silica slurry prepared above is mixed in 5 gallon bucket to reach the target of slurry with the desired amount of deionized water Silica concentration.

For each operation described below, the silica slurry that specified amount is taken out in tank is run from slurry, and in 5 gallon bucket In, mixed with the elastomer latices of specified amount 15 minutes-use overhead type low sheraing blender (#1750 types, Arrow Engineering Co, Inc., Hillside, NJ).Other than in operation 5, calcium chloride salt is then added to mixture In and continue mixing until cohesion seem to complete.Unless otherwise stated, salt is with the 20wt% salting liquids in deionized water Form is added.Salt amount (dry measure) used is as follows.Assuming that all silicas are all incorporated into all rubber, then " target silica Phr " reflects the amount (unit phr) of the expected silica being present in rubber composite, the starting based on used silica Amount.The method of B according to the method described above is dehydrated and is dried to operation 1-4.

Operation 1-uses the rubber composite of the target 55phr silicas of 25wt% silica slurries.

Condition (is directed to about 1.9kg dry matters)：

The 25wt% silica slurries of 2.7kg, it is ground

4.0kg latex concentration objects

The salt in the solution of 0.060kg (equivalent amount of dry matter).

Observed result：After the completion of cohesion, the wet rubber composite of bulk is formed around stirring blade.However, cohesion does not have Have and all rubber and silica are attached in condensation product, because emulsion liquid is retained in tempering tank, and one layer of wet silica Deposition is on the bottom of the tub.Condensation product after drying weighs about 0.5 kilogram, is far below 1.9 kilograms of target output.Rubber product table Occur a large amount of silicas on face, shows that distribution of the silica in rubber composite is poor.In condensation product, silica seems and rubber mix Must be excessively poor, moreover, can feel and see the particle of silica not being dispersed through in entire condensation product.Observe silica Grain is fallen from dry condensation product.When the rubber product dried using scissors cut, silica granule is fallen from cutting surfaces.Dry After dry, the TGA of rubber product is analysis shows the average loading capacity of silica is about 44phr.

Operation 2-uses the rubber composite of the target 70phr silicas of 25wt% silica slurries.

Condition (is directed to about 1.9kg dry matters)：

The 25wt% silica slurries of 3.1kg, it is ground

3.6kg latex concentration objects

0.060kg salt is added as dry matter.

Observed result：The wet rubber of bulk is formed around hybrid blade, moreover, rear coagulation liquid is in muddy or milky. There are one layer of silicas on bucket bottom.Generate about 1 kilogram of dry condensation product.It is similar with operation 1, observe that silica granule is agglomerated in rubber Distribution in object is excessively poor.After the drying, the TGA of rubber product is analysis shows that the average loading capacity of silica is about 53phr.

Operation 3-uses the rubber composite of the target 55phr silicas of 6wt% silica slurries.

Condition (is directed to about 2kg dry matters)：

The 25wt% silica slurries of 2.6kg, it is ground

8.4kg deionized water

4.0kg latex concentration objects

The salt in the solution of 0.090kg.

Observed result：After salt is added, the entire mixture of latex and slurry becomes soft gel.The dry of about 0.9kg is made Dry compound.It is similar with operation 1, observe that distribution of the silica granule in rubber condensation product is excessively poor.After the drying, by TGA Silica loading capacity in the condensation product measured is about 45phr.

Operation 4-uses the rubber composite of the target 70phr silicas of 6wt% silica slurries.

Condition (is directed to about 2kg dry matters)：

The 25wt% silica slurries of 3.1kg, it is ground

9.9kg water

The latex concentration object of 3.7kg

The salt in the solution of 0.10kg.

Observed result：After salt is added, small clast is formed in emulsion liquid.Sieve is used to collect and compress this small broken Bits.It is similar with operation 1, observe that dispersion of the silica granule in rubber condensation product is excessively poor.The drying for being collected into about 0.7kg is multiple Object is closed, and is about 50phr by the silica loading capacity in clast that TGA is measured.

5 uses are run with 1%CaCl₂The rubber of the target 55phr silicas of the 25wt% silica slurries of stabilization removal is compound Object.

Condition (is directed to about 1.9kg dry matters)：

4.0kg's contains 1%CaCl₂25wt% slurries, it is ground

The latex concentration object of 2.7kg.

Observed result：Latex is put into 5 gallon bucket stirred with overhead type low sheraing.1% will be contained under stiring CaCl₂The silica slurry of 25% ground stabilization removal pour into the bucket, and continue stirring until cohesion is completed.To rubber The vision and tactile observations of sheet material are shown：Silica slurry in rubber sheet permitted great pouch-shaped construction (size be millimeter extremely Centimetre) and largely silica granule is captured but is not distributed in solid rubber phase.Average silicon in the dry condensation product that TGA is measured Stone loading capacity is about 58phr.Silica loading capacity variation between sample and sample is more than 10phr.

Test 8-B：Use the batch-mixed of not ground silica slurry.

In order to prepare not ground silica slurry, overhead type stirrer (#1750 types, Arrow is used only Engineering Co, Inc., Hillside, NJ) silica is slowly added in water.When silica seems to be completely dispersed, add Enter latex and stirs liquid mixture 20 minutes.Then by CaCl₂Salting liquid is added in liquid mixture and is mixed Until cohesion seems to complete.Before TGA analyses, sample is dried in an oven.

Run rubber compositions of the 5B-using the target 65phr silicas of 25wt% silica slurries.

Condition (is directed to about 1.9kg dry matters)：

The 25wt% silica slurries of 3.0kg

The latex concentration object of 3.8kg

The salt in the solution of 0.06kg.

Observed result：After salt is added, the rubber condensation product of very bulk is formed around the blade of blender.It is agglomerating Afterwards, thick silica layer is deposited in the bottom of bucket.Rubber block feels as gravel and is sticky.Silica particle can be in rubber It is felt and sees on the surface of condensation product, moreover, visually observation display, distribution of the silica in rubber condensation product is very Difference.Determine that the silica loading capacity in condensation product is 25phr using TGA.

Operation 6-uses the rubber composite of the target 80phr silicas of 25wt% silica slurries.

Condition (is directed to about 1.9kg dry matters)：

The 25wt% silica slurries of 3.3kg

The latex concentration object of 3.4kg

The salt in the solution of 0.06kg.

Observed result：Loading capacity of the silica in rubber is confirmed as 35phr, moreover, silica is in rubber condensation product It is distributed excessively poor.

Operation 7-uses the rubber composite of the target 110phr silicas of 6wt% silica slurries.

Condition (is directed to about 1.9kg dry matters, complete in two batches)：

The 25wt% silica slurries of 1.0kg

15.6kg water

The latex concentration object of 3.0kg

The salt in the solution of 0.120kg.

Observed result：Small rubber scraps is formd in bucket, moreover, after cohesion, remaining liquid is largely clear Clear, there is one layer of silica in the bottom of bucket.Average silica loading capacity in the rubber product that TGA is measured is about 30phr.Condensation product It is elastic, and has silica particle on surface.When dried, silica can be brushed off easily from surface, moreover, silica exists Distribution in rubber condensation product is excessively poor.

Operation 8-uses the rubber composite of the target 140phr silicas of 6wt% silica slurries.

Condition (is directed to about 1.9kg dry matters, complete in two batches)：

The 25wt% silica slurries of 1.0kg

15.7kg water

The latex concentration object of 2.4kg

The salt in the solution of 0.110kg.

Observed result：Small rubber scraps is formd in bucket, moreover, after cohesion, remaining liquid is largely clear Clear, there is one layer of silica in the bottom of bucket.Average silica loading capacity in the rubber product that TGA is measured is about 35phr.Silica Grain is deposited on the surface of rubber product, and when dried, silica granule can be brushed off, moreover, silica is in rubber condensation product Distribution it is excessively poor.

The summary of observed result.It is right compared with the method for continuous production of the elastomeric compound in such as embodiment 5 and 7 The intermittent latex mixed method of ratio 8 cannot reach the quality or quantity of silica dispersion needed for rubber.Use warp The silica slurry of grinding, is observed, with the actual silica loading capacity in the rubber product of batch-mixed production<55phr. After cohesion, the deposition of silica of significant quantity is in the bottom of tempering tank and appears on the surface of rubber product, shows that silica granule exists The capture of difference in rubber condensation product.Using not ground silica slurry, with the reality in the rubber of batch-mixed production Silica loading capacity is limited in 30phr to 35phr.After cohesion, thick silica layer is deposited in the bottom of tempering tank, in condensation product In, silica seems that the mixing with rubber is excessively poor, also, in entire condensation product, feel and see silica without point Scattered particle.With according to embodiments of the present invention for compared with producing the preferred method of elastomeric compound, batch-mixed Method makes combination and polar distribution of field poor distribution of the silica granule in the rubber matrix of condensation product.In the respective of these batch-mixeds operation Product in, observe that silica granule is fallen from dry condensation product.When the rubber composite dried using scissors cut, silica Particle is fallen from cutting surfaces.It is generated when examining the preferred method for producing elastomeric compound by embodiment of the present invention The silica containing solid-state or semisolid continuous rubber phase when, such loss of silica granule is not observed.

Fig. 3 depicts the vulcanized elastomeric compound of the sample (star) of comparative example 1 and the operation 1-4 of comparative example 8 Engineering properties (Fig. 3 A-T300/T100 modular ratios, Fig. 3 B- tensile strengths (MPa), the figure of (triangle) relative to silica loading capacity 3C-tan δ 60 and Fig. 3 D- elongation at break (%) * tensile strengths (MPa)).In the various figures, meet equation T300/T100 >=- 0.024s+6.3 (Fig. 3 A), tensile strength (MPa >=-0.21s+41 (Fig. 3 B), 60≤0.0022s-0.05 of tan δ (Fig. 3 C) or Elongation at break (%) * tensile strengths (MPa) >=-211s+27543 (Fig. 3 D) (wherein s is the silica loading capacity that unit is phr) The sample of embodiment 5 be plotted as diamond shape.The figure shows, improved engineering properties usually in continuous wet method master batch method Related using one or more latex concentration objects and/or salt, acid is as additional destabilizing agent whether or not using.Compared to it Under, the method for comparative example 8 cannot produce the rubber for meeting in above-mentioned equation the high-quality for being more than a standard always.

Fig. 4 depict the sample (star) of comparative example 1, comparative example 8 operation 1-4 vulcanized elastomeric compound Modular ratio (T300/ of the vulcanized elastomeric compound (diamond shape) of (triangle) and embodiment 5 relative to 60 values of tan δ T100).The chart is bright, can realize that high-modulus ratio (is more than according only to the elastomeric compound of embodiment of the present invention And both tan δ (be less than 0.05) (box 301) 5.5).Since modular ratio is usually reduced with loading capacity, it is higher The silica elastomeric compound of loading capacity can show performance desirably in the case where not meeting these standards.

Fig. 5 depicts modular ratio (T300/ of the vulcanized elastomeric compound relative to expansion index of embodiment 5 T100；Diamond shape) and tan δ 60 (square).Expansion index in (being enough to cover sample) toluene by cultivating 0.5g samples It 120 hours measures, wherein replace toluene after 48 hrs.Sample is weighed with the weight after be swollen, environment temperature with It is dried overnight under pressure, is then stayed overnight again in 50 DEG C of vacuum drying oven, hereafter, weigh sample to obtain dry weight.Expansion refers to Number is the difference divided by dry weight between weight and dry weight after swelling.The chart is bright, expansion index be about 1.80~about Under conditions of 2.20 (particularly from about 1.90~about 2.10), optimize to provide the high-modulus ratio of vulcanized elastomeric compound. Therefore, vulcanized elastomeric compound can be optimized by adjusting expansion index (such as type by adjusting accelerating agent) Engineering properties combination.

Embodiment 9

In these embodiments, using method A as described above or method B, in various operating conditions as described in Table 8 Under, the method for operation production silica elastomeric compound on the device shown in Fig. 1 ((a) or (b)).Selection operation condition with Generate the continuous rubber phase containing silica of the ratio with silica and rubber described in table 8.In each example, contain silica Continuous rubber phase include at least aqueous fluids of 40wt%.The approximation of the continuous rubber phase containing silica occurred from reaction zone is disconnected Elongation is split to be also given in Table 8.

Table 8

8 (Continued) of table

N/A=is not applicable

ND=is not measured

A. embodiment 9-17 uses 400 silicas of Agilon (deriving from PPG Industries Inc.).All other realities Example is applied to useZ1165MP precipitated silicas.

B. zeta potential value by the determining zeta potential of experiment and the salt of the slurry of same levels silica or the concentration of acid according to It deposits relation curve and carries out interpolation method to be estimated.

C. inlet nozzle speed is that silica slurry is reached before contacting latex by the nozzle (3a) at first entrance (3) Speed when reaction zone (13).

D. the flow rate of slurry and latex is silica slurry and latex fluids respectively when they are transported to reaction zone The rate of volume flow in terms of L/ hours.

The result shows that the elastomeric continuous rubber containing silica of solid article form may be implemented in every operating condition Glue phase material.Higher elongation with below in connection with：The use of latex concentration object, lower throughput rate are (based on dry matter Flow rate of material), the silica slurry of increased residence time, and/or latex and/or stabilization removal in the reaction region compared with Low flow rate.

Embodiment 10.

In these embodiments, the method for various embodiment production elastomeric compounds according to the present invention is in Fig. 1 (a) Shown in carried out under the conditions of as described in Table 9 various in device, utilize method A and fresh latex.Embodiment 10-4 is used The silica slurry of 10wt%；All other samples use 20% silica slurry to produce.All embodiments useZ1165MP precipitated silicas.Selection operation condition is to generate the ratio with silica and rubber described in table 9 The continuous rubber phase of the silica containing solid-state or semisolid.Sample is dehydrated according to method A, additional take off then is carried out according to method B Water and drying, without adding coupling agent or antioxidant.

Table 9

A. all embodiments using salt use calcium nitrate.

B. all embodiments using acid use acetic acid

9 (Continued) of table

In all embodiments, selected operating condition all produces substantial cylindrical silica containing solid-state or semisolid Continuous rubber phase.When squeezed, which keeps coherent, solids content is kept to be discharged side by side.The product contains The water of more amount has elasticity and compressibility, and water is discharged in manual compression and keeps solids content.Observe silicon Stone particle is uniformly distributed in entire continuous rubber phase, and the product all there is no on outer surface and inner surface it is free Silica granule and larger silica particle.As shown in fig. 6, being prepared compared to by the mixing of dry silica and dry rubber Elastomeric compound (correspond to star in Fig. 6), using the logistics and elastomer of the silica slurry for wherein making stabilization removal The method of latex combination provides the improvement in terms of enhancing.It is listed in Table 9 below and (water chestnut of the embodiment of the present invention shown in Figure 6 Shape) modular ratio (T300/T100) for being equal to or more than -0.025s+6.2 is all had, wherein s is silica loading capacity.

The present invention includes following aspect/embodiment/feature with random order and/or in any combination：

The elastomeric compound that can vulcanize, it includes at least silicas of 40phr being dispersed in natural rubber, wherein When the elastomeric compound that can vulcanize vulcanizes, the sulfur product of gained shows at least T300/ of -0.024s+b T100 ratios, wherein s are the silicas in the elastomeric compound that can vulcanize indicated with the weight rubber (phr) of part/100 Amount and b are 6.3, and, at least one additional property selected from the following

A) the tan δ 60 of at most 0.0022s-c, wherein c are 0.05；

B) tensile strength that at least unit of -0.21s+d is MPa, wherein d are 41；

C) at least elongation at break of -211s+e (%) * tensile strengths (MPa), wherein e=27543；With

D) at least 55phr for example, at least silica contents of 60phr.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the vulcanization Product shows that the T300/T100 ratios of at least -0.024s+b, wherein b are 6.4,6.6 or 6.8.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the vulcanization Product shows that the tan δ 60 of at most 0.0022s-c, wherein c are 0.06.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the vulcanization Product shows that the tensile strength that at least unit of -0.21s+d is MPa, wherein d are 41.4.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the vulcanization Product shows the T300/T100 ratios from -0.024s+b at most 7.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this can The elastomeric compound of vulcanization includes the silica for being up to about 180phr or up to about 100phr.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this can The elastomeric compound of vulcanization includes the carbon black of up to 10wt%, relative to the enhancing in the elastomeric compound that can vulcanize The total weight of particle.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the vulcanization Product shows the tan δ 60 from 0.02 to 0.0022s-c.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the vulcanization Product is shown from -0.21s+d to 40 or the tensile strength of 35MPa.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the vulcanization Product shows elongation at break (%) the * tensile strengths (MPa) from -211s+e to 21500.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the silica Including with about 20m²/ g~about 450m²/ g is (for example, about 120~about 225m²/g、20m²/ g~about 450m²/ g, about 30m²/ g~ About 450m²/ g, about 30m²/ g~about 400m²/ g, about 120m²/ g~about 225m²/ g, about 80m²/ g~about 200m²/ g or about 60m²/ G~about 250m²/ g) surface area precipitated silica, the surface area measured by N2 adsorption.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this can The elastomeric compound of vulcanization includes the wet method masterbatch through dehydration for the silica being dispersed in as slurry in natural rubber latex.

Vulcanized elastomeric compound, it includes capable of vulcanizing for arbitrary aforementioned or subsequent implementation mode/feature/aspect Elastomeric compound sulfur product, optionally have about 1.80~about 2.20 (for example, about 1.90~about 2.10 or about 1.95 ~expansion index about 2.05).

The elastomeric compound that can vulcanize, it includes at least silicas of 55phr being dispersed in natural rubber, wherein When the elastomeric compound that can vulcanize vulcanizes, the sulfur product of gained shows at least 5 T300/T100 ratios Rate.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this can The elastomeric compound of vulcanization includes at least silica of 60phr.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the vulcanization Product shows at least elongation at break of -211s+e (%) * tensile strengths (MPa), wherein e=27543 and s is that unit is The silica loading capacity of phr.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the vulcanization Product shows at most 7 T300/T100 ratios.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this can The elastomeric compound of vulcanization includes the silica of up to 180phr or up to 100phr.

Vulcanized elastomeric compound, it includes capable of vulcanizing for arbitrary aforementioned or subsequent implementation mode/feature/aspect Elastomeric compound sulfur product, optionally have about 1.80~about 2.20 (for example, about 1.90~about 2.10 or about 1.95to 2.05) expansion index.

The elastomeric compound that can vulcanize, it includes the silicas being dispersed in natural rubber, for example, at least 40phr Silica, wherein when the elastomeric compound that can vulcanize vulcanizes, the sulfur product of gained shows at least 6.3 T300/T100 ratios.

The elastomeric compound that can vulcanize, it includes at least 40phr being dispersed in natural rubber (for example, at least Silica 50phr), wherein when the elastomeric compound that can vulcanize vulcanizes, there is at least -0.025s+6.2 The T300/T100 ratios of (for example, at least -0.025s+6.3 or 6.4).The elastomeric compound that can vulcanize may include as slurry Material is dispersed in the wet method masterbatch through dehydration of silica in fresh latex, can for example, by using ammonia, removal sludge or chemistry or Enzyme modification and it is stabilized.

The elastomeric compound that can vulcanize, it includes the silicas being dispersed in natural rubber, for example, at least 40 or The silica of 55phr, wherein when the elastomeric compound that can vulcanize vulcanizes, the sulfur product of gained show to Few 5.5 T300/T100 ratios and at most 0.05 tan δ 60.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this can The elastomeric compound of vulcanization includes at least silica of 55phr.

The elastomeric compound that can vulcanize of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the vulcanization Product shows at least 0.02 tan δ 60.

Vulcanized elastomeric compound, it includes capable of vulcanizing for arbitrary aforementioned or subsequent implementation mode/feature/aspect Elastomeric compound sulfur product, optionally have about 1.80~about 2.20 (for example, about 1.90~2.10 or about 1.95~ 2.05) expansion index.

Vulcanized elastomeric compound, it includes at least silicas of 40phr being dispersed in natural rubber, wherein should Vulcanized elastomeric compound show it is following in it is one or more：

A) the T300/T100 ratios of at least -0.024s+b, wherein s be with the weight rubber (phr) of part/100 indicate should The amount and b of silica in vulcanized elastomeric compound are 6.3, and, the tan δ 60 of at most 0.0022s-c, wherein c are 0.05；

B) the silica loading capacity of at least 5 T300/T100 ratios and at least 55phr；

C) at least 6.3 T300/T100 ratios；With

D) the T300/T100 ratios of at least -0.024s+b, wherein s be with the weight rubber (phr) of part/100 indicate should The amount and b of silica in vulcanized elastomeric compound are 6.3, and, at least the unit of -0.21s+d is that the stretching of MPa is strong Degree, wherein d are 41.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound show that the T300/T100 ratios of at least -0.024s+b, wherein b are 6.4,6.6 or 6.8.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound show that the tan δ 60 of at most 0.0022s-c, wherein c are 0.06.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound show that at least unit of -0.21s+d is the tensile strength of MPa, wherein d is 41.4.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound include up to 180phr or up to 100phr silica.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound include at least silica of 55phr.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound include up to 10wt% carbon black, relative to the particle filler in the vulcanized elastomeric compound Weight.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound show at most 7 T300/T100 ratios.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound show at least 0.02 tan δ 60.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound show the tensile strength of at most 40 or 35MPa.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound show at least elongation at break of -211s+e (%) * tensile strengths (MPa), wherein e=27543.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound show at most 21500 elongation at break (%) * tensile strengths (MPa).

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein the silica packet Containing with about 20m²/ g~about 450m²/ g is (for example, about 120~about 225m²/g、20m²/ g~about 450m²/ g, about 30m²/ g~about 450m²/ g, about 30m²/ g~about 400m²/ g, about 120m²/ g~about 225m²/ g, about 80m²/ g~about 200m²/ g or about 60m²/g ~about 250m²/ g) surface area precipitated silica, the surface area measured by N2 adsorption.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound include the wet method masterbatch through dehydration that silica in natural rubber latex is dispersed in as slurry vulcanization Product.

The vulcanized elastomeric compound of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein this is through vulcanization Elastomeric compound have about 1.80~about 2.20 (for example, about 1.90~about 2.10 or about 1.95~about 2.00) expansion refer to Number.

The elastomeric compound that can vulcanize or vulcanized bullet of arbitrary aforementioned or subsequent implementation mode/feature/aspect Elastomer composite, wherein the silica includes precipitated silica.

The continuous rubber phase product of the silica containing solid-state, it includes at least 40 parts/100 rubber being dispersed in natural rubber (phr) aqueous fluids of silica and at least 40wt%, wherein the continuous rubber phase product for containing solid-state silica is shown at least About 100% elongation at break.

The continuous rubber phase product of the silica containing solid-state of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein should The continuous rubber phase product of the silica containing solid-state shows about 100%~about 600% (for example, 100%~about 600%, such as, about 120%~about 200%, about 100%~about 150%, about 130%~about 250%, about 150%~about 200%, about 200%~about 300%, about 300%~about 600%, about 300%~about 500% or about 300%~elongation at break about 400%).

The continuous rubber phase product of the silica containing solid-state of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein should The continuous rubber phase product of the silica containing solid-state include about 40~about 180phr or about 40~about 100phr (for example, about 50phr~about Silica 150phr).

The continuous rubber phase product of the silica containing solid-state of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein should Silica includes to have about 20m²/ g~about 450m²/ g is (for example, about 120~about 225m²/g、20m²/ g~about 450m²/ g, about 30m²/ G~about 450m²/ g, about 30m²/ g~about 400m²/ g, about 120m²/ g~about 225m²/ g, about 80m²/ g~about 200m²/ g or about 60m²/ g~about 250m²/ g) surface area precipitated silica, the surface area measured by N2 adsorption.

The continuous rubber phase product of the silica containing solid-state of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein should The continuous rubber phase product of the silica containing solid-state includes the carbon black of up to 10wt%, the continuous rubber phase relative to the silica containing solid-state The total weight of enhancing particle in product.

The continuous rubber phase product of the silica containing solid-state of arbitrary aforementioned or subsequent implementation mode/feature/aspect, wherein should The continuous rubber phase product of the silica containing solid-state include about 40%~about 90wt% (for example, about 50%~about 85% or about 60%~ About 80%) water.

The present invention may include these the above and/or following various features such as illustrated with sentence and/or paragraph or embodiment party The arbitrary combination of formula.The arbitrary combination of feature disclosed herein is considered as the part of the present invention and for that can combine Feature is not intended to restricted.

The full content of the reference literature of all references is clearly introduced into present disclosure by applicant.Further Ground, the list of equivalent, concentration or other values or parameter as range, preferred scope or higher preferred value and relatively low preferred value When providing, this should be understood to specifically disclose by arbitrary higher range boundary or preferred value and arbitrary relatively low range limit or Preferred value it is arbitrary to being formed by all ranges, whether individually disclosed without scope tube.When narration numerical value model herein When enclosing, unless otherwise stated, the range is intended to encompass its endpoint and all integers in the range and score (part).The scope of the present invention is not intended to be limited to the particular value described in the range of definition.

By to this specification thinking and the present invention disclosed herein practice, other embodiments of the present invention for To be apparent for those skilled in the art.It is intended that this specification and embodiment are to be considered merely as illustrative, and this The true scope and spirit of invention are indicated by appended claims and its equivalent.

Claims

1. the elastomeric compound that can vulcanize, it includes at least silicas of 40phr being dispersed in natural rubber, wherein when When the elastomeric compound that can vulcanize vulcanizes, the sulfur product of gained shows at least T300/ of -0.024s+b T100 ratios, wherein s are the silicas in the elastomeric compound that can vulcanize indicated with the weight rubber (phr) of part/100 Amount and b are 6.3, and, at least one additional property selected from the following

A. the tan δ 60 of at most 0.0022s-c, wherein c are 0.05；

B. the tensile strength that at least unit of -0.21s+d is MPa, wherein d are 41；

C. at least elongation at break of -211s+e (%) * tensile strengths (MPa), wherein e=27543；With

D. at least 55phr for example, at least silica contents of 60phr.

2. the elastomeric compound that can vulcanize of claim 1, wherein the sulfur product shows at least -0.024s+b's T300/T100 ratios, wherein b are 6.8.

3. the elastomeric compound that can vulcanize of claims 1 or 2, wherein the sulfur product shows at most 0.0022s-c Tan δ 60, wherein c be 0.06.

4. the elastomeric compound that can vulcanize of any one of claim 1-3, wherein the sulfur product show at least- The unit of 0.21s+d is the tensile strength of MPa, and wherein d is 41.4

5. the elastomeric compound that can vulcanize of any one of claim 1-4, wherein the sulfur product shows at most 7 T300/T100 ratios.

6. the elastomeric compound that can vulcanize of any one of claim 1-5, wherein the elastomer composite that can vulcanize Object includes the silica for being up to about 180phr.

7. the elastomeric compound that can vulcanize of any one of claim 1-6, wherein the elastomer composite that can vulcanize Object includes the carbon black of up to 10wt%, the total weight relative to the enhancing particle in the elastomeric compound that can vulcanize.

8. the elastomeric compound that can vulcanize of any one of claim 1-7, wherein the sulfur product is shown at least 0.02 tan δ 60.

9. the elastomeric compound that can vulcanize of any one of claim 1-8, wherein the sulfur product shows at most 40 Or the tensile strength of 35MPa.

10. the elastomeric compound that can vulcanize of any one of claim 1-9, wherein the sulfur product is shown at most 21500 elongation at break (%) * tensile strengths (MPa).

11. the elastomeric compound that can vulcanize of any one of claim 1-10, wherein the silica includes to have about 20m²/ G~about 450m²The precipitated silica of the surface area of/g, the surface area are measured by N2 adsorption.

12. the elastomeric compound that can vulcanize of any one of claim 1-11, wherein the elastomer that can vulcanize is multiple Close the wet method masterbatch through dehydration that object includes the silica being dispersed in as slurry in natural rubber latex.

13. vulcanized elastomeric compound includes the elastomeric compound that can vulcanize of any one of claim 1-12 Sulfur product, optionally with about 1.80~about 2.20 expansion index.

14. the elastomeric compound that can vulcanize, it includes the silicas being dispersed in natural rubber, wherein when this can vulcanize Elastomeric compound when vulcanizing, the sulfur product of gained shows at least 6.3 T300/T100 ratios.

15. the elastomeric compound that can vulcanize of claim 14, including at least silica of 40phr.

16. the elastomeric compound that can vulcanize, it includes at least silicas of 55phr being dispersed in natural rubber, wherein when When the elastomeric compound that can vulcanize vulcanizes, the sulfur product of gained shows at least 5 T300/T100 ratios.

17. the elastomeric compound that can vulcanize of any one of claim 14-16, wherein the elastomer that can vulcanize Compound includes the wet method masterbatch through dehydration for the silica being dispersed in as slurry in natural rubber latex.

18. the elastomeric compound that can vulcanize, it includes at least silicas of 40phr being dispersed in natural rubber, wherein when When the elastomeric compound that can vulcanize vulcanizes, the T300/T100 ratios at least -0.025s+6.2.

19. the elastomeric compound that can vulcanize of claim 18, wherein the elastomeric compound that can vulcanize includes to make The wet method masterbatch through dehydration of the silica in fresh latex is dispersed in for slurry.

20. the elastomeric compound that can vulcanize of any one of claim 14-19, wherein the elastomer that can vulcanize Compound includes at least silica of 60phr.

21. the elastomeric compound that can vulcanize of any one of claim 14-20, wherein the sulfur product show to Elongation at break (%) the * tensile strengths (MPa) of few -211s+e, wherein e=27543 and s are the silica load that unit is phr Amount.

22. the elastomeric compound that can vulcanize of any one of claim 14-21, wherein the sulfur product show to More 7 T300/T100 ratios.

23. the elastomeric compound that can vulcanize of any one of claim 14-22, wherein the elastomer that can vulcanize Compound includes the silica of up to 180phr.

24. the elastomeric compound that can vulcanize of any one of claim 14-23, wherein the elastomer that can vulcanize Compound includes the carbon black of up to 10wt%, the gross weight relative to the enhancing particle in the elastomeric compound that can vulcanize Amount.

25. the elastomeric compound that can vulcanize of any one of claim 14-24, wherein the silica includes to have about 20m²/ g~about 450m²The precipitated silica of the surface area of/g, the surface area are measured by N2 adsorption.

26. vulcanized elastomeric compound, it includes the elastomer composites that can vulcanize of any one of claim 14-25 The sulfur product of object, optionally with about 1.80~about 2.20 expansion index.

27. the elastomeric compound that can vulcanize, it includes the silicas being dispersed in natural rubber, wherein when this can vulcanize Elastomeric compound when vulcanizing, the sulfur product of gained shows at least 5.5 T300/T100 ratios and at most 0.05 Tan δ 60.

28. the elastomeric compound that can vulcanize of claim 27, wherein the elastomeric compound that can vulcanize includes extremely The silica of few 40phr.

29. the elastomeric compound that can vulcanize of claim 27 or 28, wherein the sulfur product shows at least 0.02 tanδ60。

30. the elastomeric compound that can vulcanize of any one of claim 27-29, wherein the sulfur product show to More 7 T300/T100 ratios.

31. the elastomeric compound that can vulcanize of any one of claim 27-30, wherein the elastomer that can vulcanize Compound includes at least silica of 55phr.

32. the elastomeric compound that can vulcanize of any one of claim 27-31, wherein the elastomer that can vulcanize Compound includes the carbon black of up to 10wt%, the gross weight relative to the enhancing particle in the elastomeric compound that can vulcanize Amount.

33. the elastomeric compound that can vulcanize of any one of claim 27-32, wherein the silica includes to have about 20m²/ g~about 450m²The precipitated silica of the surface area of/g, the surface area are measured by N2 adsorption.

34. the elastomeric compound that can vulcanize of any one of claim 27-33, wherein the elastomer that can vulcanize Compound includes the wet method masterbatch through dehydration for the silica being dispersed in as slurry in natural rubber latex.

35. vulcanized elastomeric compound, it includes the elastomer composites that can vulcanize of any one of claim 27-34 The sulfur product of object, optionally with about 1.80~about 2.20 expansion index.

36. vulcanized elastomeric compound, it includes at least silicas of 40phr being dispersed in natural rubber, wherein the warp The elastomeric compound of vulcanization show it is following in it is one or more：

A. the T300/T100 ratios of at least -0.024s+b, wherein s be indicated with the weight rubber (phr) of part/100 this through sulphur The amount and b of silica in the elastomeric compound of change are 6.3, and, the tan δ 60 of at most 0.0022s-c, wherein c are 0.05；

B. the silica loading capacity of at least 5 T300/T100 ratios and at least 55phr；

C. at least 6.3 T300/T100 ratios；With

D. the T300/T100 ratios of at least -0.024s+b, wherein s be indicated with the weight rubber (phr) of part/100 this through sulphur The amount and b of silica in the elastomeric compound of change are 6.3, and, at least the unit of -0.21s+d is the tensile strength of MPa, Wherein d is 41.

37. the vulcanized elastomeric compound of claim 36, wherein the vulcanized elastomeric compound show to The T300/T100 ratios of few -0.024s+b, wherein b are 6.8.

38. the vulcanized elastomeric compound of any one of claim 36-37, wherein the vulcanized elastomer composite Object shows that the tan δ 60 of at most 0.0022s-c, wherein c are 0.06.

39. the vulcanized elastomeric compound of any one of claim 36-38, wherein the vulcanized elastomer composite Object shows that the tensile strength that at least unit of -0.21s+d is MPa, wherein d are 41.4.

40. the vulcanized elastomeric compound of any one of claim 36-39, wherein the vulcanized elastomer composite Object includes the silica of up to 180phr.

41. the vulcanized elastomeric compound of any one of claim 36-40, wherein the vulcanized elastomer composite Object includes at least silica of 55phr.

42. the vulcanized elastomeric compound of any one of claim 36-41, wherein the vulcanized elastomer composite Object includes at least silica of 60phr.

43. the vulcanized elastomeric compound of any one of claim 36-42, wherein the vulcanized elastomer composite Object includes the carbon black of up to 10wt%, the weight relative to the particle filler in the vulcanized elastomeric compound.

44. the vulcanized elastomeric compound of any one of claim 36-43, wherein the vulcanized elastomer composite Object shows at most 7 T300/T100 ratios.

45. the vulcanized elastomeric compound of any one of claim 36-44, wherein the vulcanized elastomer composite Object shows at least 0.02 tan δ 60.

46. the vulcanized elastomeric compound of any one of claim 36-45, wherein the vulcanized elastomer composite Object shows the at most tensile strength of 40MPa.

47. the vulcanized elastomeric compound of any one of claim 36-46, wherein the vulcanized elastomer composite Object shows at least elongation at break of -211s+e (%) * tensile strengths (MPa), wherein e=27543.

48. the vulcanized elastomeric compound of claim 47, wherein the vulcanized elastomeric compound is shown at most 21500 elongation at break (%) * tensile strengths (MPa).

49. the vulcanized elastomeric compound of any one of claim 36-48, wherein the silica includes to have about 20m²/g ~about 450m²The precipitated silica of the surface area of/g.

50. the vulcanized elastomeric compound of any one of claim 36-49, wherein the vulcanized elastomer composite Object includes the sulfur product of the wet method masterbatch through dehydration for the silica being dispersed in as slurry in natural rubber latex.

51. the vulcanized elastomeric compound of any one of claim 36-50, wherein the vulcanized elastomer composite Object has about 1.80~about 2.20 expansion index.

52. the vulcanized elastomeric compound of any one of claim 36-51, wherein the silica includes precipitated silica.

53. the continuous rubber phase product of the silica containing solid-state, it includes at least 40 parts/100 rubber being dispersed in natural rubber (phr) aqueous fluids of silica and at least 40wt%, wherein the continuous rubber phase product for containing solid-state silica is shown at least About 100% elongation at break.

54. the continuous rubber phase product of the silica containing solid-state of claim 53, wherein this contains the continuous rubber phase system of solid-state silica Product show about 100%~about 600% elongation at break.

55. the continuous rubber phase product of the silica containing solid-state of claim 53 or 54, wherein this contains the continuous rubber of solid-state silica Phase product includes about 40~about 180phr.

56. the continuous rubber phase product of the silica containing solid-state of any one of claim 53-55, wherein the silica includes to have About 20m²/ g~about 450m²The precipitated silica of the surface area of/g.

57. the continuous rubber phase product of the silica containing solid-state of any one of claim 53-56, wherein this contains solid-state silica Continuous rubber phase product includes the carbon black of up to 10wt%, relative to the enhancing in the continuous rubber phase product of the silica containing solid-state The total weight of particle.

58. the continuous rubber phase product of the silica containing solid-state of any one of claim 53-57, wherein this contains solid-state silica Continuous rubber phase product includes the water of about 40%~about 90wt%.

59. the elastomeric compound that can vulcanize of claim 19, wherein the fresh latex is by removal sludge or chemistry Or enzyme modification, alternatively, including the ammonia being added.

60. the elastomeric compound that can vulcanize of any one of claim 1-12,14-25 and 27-34, wherein the silicon Stone is precipitated silica.